WO2021047588A1 - Tall oil fatty acid imidazoline sulfonate surfactant and preparation method therefor - Google Patents

Tall oil fatty acid imidazoline sulfonate surfactant and preparation method therefor Download PDF

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WO2021047588A1
WO2021047588A1 PCT/CN2020/114502 CN2020114502W WO2021047588A1 WO 2021047588 A1 WO2021047588 A1 WO 2021047588A1 CN 2020114502 W CN2020114502 W CN 2020114502W WO 2021047588 A1 WO2021047588 A1 WO 2021047588A1
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tall oil
fatty acid
oil fatty
imidazoline
acid
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PCT/CN2020/114502
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French (fr)
Chinese (zh)
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张威
张高飞
王丰收
刘兵
徐福利
司丽丽
李蕊
韩建英
陶源
汪传新
武先东
李森
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中国日用化学研究院有限公司
上海发凯化工有限公司
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Priority claimed from CN201910857979.7A external-priority patent/CN110721634A/en
Priority claimed from CN201910857434.6A external-priority patent/CN110694546A/en
Application filed by 中国日用化学研究院有限公司, 上海发凯化工有限公司 filed Critical 中国日用化学研究院有限公司
Publication of WO2021047588A1 publication Critical patent/WO2021047588A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton

Definitions

  • the invention belongs to the technical field of surfactants, and specifically relates to a tall oil fatty acid imidazoline sulfonate surfactant and a preparation method.
  • Tall oil fatty acids are composed of straight-chain fatty acids with C 16 and C 18 chain lengths. The main components are unsaturated fatty acids such as oleic acid and linoleic acid, and a small amount of saturated palmitic acid, stearic acid and rosin acid.
  • Tall oil The source of fatty acids is very rich. It is obtained by distillation and separation of crude tall oil.
  • Tall oil also known as tall oil, tall oil
  • Tall oil is a by-product of pine alkali pulping. At present, the use of tall oil directly as a raw material is rarely used, and its utilization accounts for about 10% of the total crude tall oil. The vast majority of crude tall oil is separated through multiple stages, and then these raw materials are made into other products. .
  • Imidazoline surfactant is a surfactant with excellent application performance. It can produce good synergistic effects when compatible with almost all other types of surfactants. It can be used in daily chemical industry, metal corrosion inhibition, petroleum exploitation, textile, printing and dyeing, etc. The field has very broad application prospects. Today, the most sold imidazoline surfactant product on the market is imidazoline lauric acid with a content of about 35%. BASF, Guangzhou Tianci, Guangzhou Xingye, Shanghai Fakai, etc.
  • Tall oil fatty acids are mainly composed of long carbon chain straight chain fatty acids, and imidazoline products synthesized with it will have greater viscosity. The complexity of tall oil fatty acid composition also places high requirements on the product process.
  • the present invention uses tall oil fatty acids derived from the by-products of the pine wood paper industry as raw materials to prepare a tall oil fatty acid imidazoline sulfonate surfactant. It provides a new route for the deep processing of tall oil products in our country, which can greatly improve the utilization rate of tall oil products, increase the added value of products, and have significant economic and social benefits.
  • tall oil fatty acid and hydroxyethyl ethylenediamine as raw materials, and used xylene as a water-carrying agent to synthesize a tall oil acid imidazoline intermediate, which was then combined with 3-chloro-2-hydroxyl Sodium propanesulfonate synthesizes tall oil sulfonate.
  • xylene is a type 3 carcinogenic solvent, which is not conducive to industrial promotion ( S.-F.Wang,T.Furuno,Z.Cheng.Synthesis of 1-hydroxyethyl-2-alkyl-2-imidazoline and its derivative sulfonate amhotericsurfactant from tall oil fatty acid.J.Wood Sci.49(2003)371 -376.).
  • the purpose of the present invention is to provide a tall oil Fatty acid imidazoline sulfonate surfactant and preparation method.
  • the invention deep-processes tall oil fatty acid resources, a by-product of the pulp and paper industry, and reuses the resources to prepare a tall oil fatty acid imidazoline sulfonic acid
  • the salt surfactant improves the viscosity of the product. This surfactant has low irritation, 100% biodegradability in 7 days, high atom utilization, high alkali resistance, good appearance and stability.
  • the first aspect of the present invention provides a tall oil fatty acid imidazoline sulfonate surfactant, the main component structural formula of which is as follows:
  • R is a tall oil fatty acid alkyl group.
  • the tall oil fatty acid imidazoline sulfonate surfactant is prepared as a raw material using commercially available tall oil fatty acids, and the main components of the commercially available tall oil fatty acids are oleic acid, linoleic acid, abietic acid and a small amount of saturated fatty acids , R is mainly the corresponding oleic acid, linoleic acid alkyl group, rosin acid alkyl group, saturated fatty acid group;
  • Trace amount of saturated fatty acid groups such as C16 acid alkyl part, C18 acid alkyl part, CH 3 (CH 2 ) 14 -CH 3 (CH 2 ) 16 -.
  • the tall oil fatty acid imidazoline sulfonate surfactant of the present invention contains the main components, water and by-products unavoidable in the preparation process, and its solid content is 30-40%, preferably 35%.
  • the second aspect of the present invention provides a preparation method of the tall oil fatty acid imidazoline sulfonate surfactant, which comprises the following steps:
  • the first step is the synthesis of tall oil acid imidazoline intermediates:
  • the tall oil fatty acid and organic polyamine are mixed, and phosphoric acid is added as a catalyst.
  • the molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1:(0.5-2):(0.005-0.05) , Adjust the vacuum residual pressure of the reaction system to 20-300mmhg, and then react with gradient heating until the anhydrous is evaporated, measure the acid value, adjust the vacuum, distill out excess raw materials, and cool down to obtain the tall oil acid imidazoline intermediate ;
  • the second step is the quaternization reaction: the tall oil acid imidazoline intermediate obtained in the first step, alkali, and deionized water are mixed, and the mass ratio of tall oil imidazoline intermediate, alkali, and deionized water is 1 :(0.1 ⁇ 0.4):(2 ⁇ 10), react with sodium alkyl sulfonate at a temperature of 40 ⁇ 100°C (preferably 60 ⁇ 90°C), the tall oil acid imidazoline intermediate and alkane
  • the molar ratio of sodium base sulfonate is 1: (1 to 3), and the reaction is performed until the chloride ion content no longer changes to obtain the tall oil fatty acid imidazoline sulfonate surfactant.
  • the organic polyamine is at least one of hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, preferably hydroxyethylethylenediamine and diethylenetriamine.
  • the molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1: (1.1 to 1.5): (0.005 to 0.01).
  • the gradient heating reaction refers to heating from room temperature to 90-110°C, heating to 160-180°C at a heating rate of 5-25°C/h for 1 to 48 hours, and heating to 210-250°C for cyclization reaction for 1 to 48 hours.
  • the acid value of the intermediate acid value is less than 3 mgKOH/g.
  • the adjusted vacuum is 2 to 3 mmhg.
  • the cooling means that the temperature is 80-100°C, preferably 90°C.
  • the base is NaOH, KOH or Na 2 CO 3 .
  • the mass ratio of the tall oil acid imidazoline intermediate, alkali, and deionized water is 1:(0.1-0.4):(3-5).
  • the molar ratio of the tall oil acid imidazoline intermediate and the sodium alkyl sulfonate is 1: (1.1-2).
  • the sodium alkyl sulfonate is sodium 3-chloro-2-hydroxypropane sulfonate, sodium 2-bromoethyl sulfonate, sodium 2-chloroethyl sulfonate, sodium allyl sulfonate, preferably 3-chloro Sodium-2-hydroxypropanesulfonate.
  • the third aspect of the present invention provides a method for preparing the tall oil fatty acid imidazoline sulfonate surfactant, which includes the following steps:
  • the first step is the synthesis of tall oil acid imidazoline intermediates:
  • the tall oil fatty acid and organic polyamine are mixed, and phosphoric acid is added as a catalyst.
  • the molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1:(0.5-2):(0.005-0.05) , Adjust the vacuum residual pressure of the reaction system to 20-300mmhg, and then react with gradient heating until the anhydrous is evaporated, measure the acid value, adjust the vacuum, distill out excess raw materials, and cool down to obtain the tall oil acid imidazoline intermediate ;
  • the second step is the quaternization reaction: the tall oil acid imidazoline intermediate obtained in the first step, lower alcohol, alkali, and deionized water are mixed, tall oil acid imidazoline intermediate, lower alcohol, alkali,
  • the mass ratio of deionized water is 1:(0.01 ⁇ 1):(0.1 ⁇ 0.4):(2 ⁇ 10), and the temperature is 40 ⁇ 100°C (preferably 60 ⁇ 90°C) with sodium alkyl sulfonate
  • the molar ratio of the tall oil acid imidazoline intermediate and the sodium alkyl sulfonate is 1: (1 to 3), and the reaction is performed until the chloride ion content no longer changes to obtain the tall oil fatty acid imidazoline sulfonic acid Salt surfactants.
  • the organic polyamine is at least one of hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, preferably hydroxyethylethylenediamine and diethylenetriamine.
  • the molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1: (1.1 to 1.5): (0.005 to 0.01).
  • the gradient heating reaction refers to heating from room temperature to 90-110°C, heating to 160-180°C at a heating rate of 5-25°C/h for 1 to 48 hours, and heating to 210-250°C for cyclization reaction for 1 to 48 hours.
  • the acid value of the intermediate acid value is less than 3 mgKOH/g.
  • the adjusted vacuum is 2 to 3 mmhg.
  • the cooling means that the temperature is 80-100°C, preferably 90°C.
  • the lower alcohol is methanol, ethanol, isopropanol or ethylene glycol, preferably ethanol or isopropanol.
  • the base is NaOH, KOH or Na 2 CO 3 .
  • the mass ratio of the tall oil acid imidazoline intermediate, lower alcohol, alkali, and deionized water is 1:(0.4 ⁇ 0.6):(0.1 ⁇ 0.4):(2.5 ⁇ 4).
  • the sodium alkyl sulfonate is sodium 3-chloro-2-hydroxypropane sulfonate, sodium 2-bromoethyl sulfonate, sodium 2-chloroethyl sulfonate, sodium allyl sulfonate, preferably 3-chloro Sodium-2-hydroxypropanesulfonate.
  • the molar ratio of the tall oil acid imidazoline intermediate and the sodium alkyl sulfonate is 1: (1.1-2).
  • the present invention has the following advantages and beneficial effects:
  • the tall oil fatty acid imidazoline sulfonate surfactant intermediate prepared by the present invention has a low content of diamide, a tall oil fatty acid (kraton FA2) conversion rate of ⁇ 98.5%, low product irritation, and a 7-day biodegradability of 100%.
  • a tall oil fatty acid (kraton FA2) conversion rate of ⁇ 98.5%
  • low product irritation and a 7-day biodegradability of 100%.
  • the deep processing of tall oil products in our country provides a new route, which can greatly improve the utilization rate of tall oil products, increase the added value of products, and have significant economic and social benefits.
  • the gradient temperature increase is to better save energy consumption, avoid excessively high temperature, too fast reaction, and produce more by-products.
  • the invention uses tall oil fatty acid as a raw material, realizes the selective control of intermediates of complex raw materials through intermediate measurement and control technology, and performs quaternization reaction with water as a solvent to obtain a tall oil fatty acid imidazoline sulfonate surfactant.
  • the invention uses tall oil fatty acid as raw material, realizes the selective regulation of complex raw material intermediates through intermediate measurement and control technology, and uses a small amount of lower alcohol and water as solvents for quaternization to obtain the surface of tall oil fatty acid imidazoline sulfonate. Active agent.
  • Figure 1 is an infrared spectrum of the tall oil fatty acid imidazoline sulfonate surfactant prepared in Example 1 of the present invention.
  • Figure 2 is an infrared spectrum of the tall oil fatty acid imidazoline sulfonate surfactant prepared in Example 11 of the present invention.
  • the reagent used in the present invention is tall oil fatty acid (kraton FA2), technical grade, purity is not standard, COA acid value: 196, rosin acid content: 0.8%, unsaponifiable matter: 1.3, iodine value: 125, color, Gardner: 3, Purchase manufacturer: Wuxi Hengmao Technology & Trade Co., Ltd.
  • R is a tall oil fatty acid alkyl group.
  • R is mainly the corresponding oleic acid, linoleic acid alkyl group, rosin acid alkyl group, and saturated fatty acid group;
  • Trace amount of saturated fatty acid groups such as C16 acid alkyl part, C18 acid alkyl part, CH 3 (CH 2 ) 14 -CH 3 (CH 2 ) 16 -.
  • the synthetic route of the present invention is as follows:
  • R is specifically:
  • Trace amount of saturated fatty acid groups such as C16 acid alkyl part, C18 acid alkyl part, CH 3 (CH 2 ) 14 -CH 3 (CH 2 ) 16 -.
  • Figure 1 is the infrared spectra of tall oil fatty acid imidazoline sulfonate surfactants prepared in Example 1 of the present invention Spectrogram.
  • the cyclization reaction is at 220°C for 3h, the acid value is 1.8mgKOH/g after anhydrous distillation, the conversion rate of tall oil fatty acid (kraton FA2) is 98.9%, the vacuum is increased to 3mmhg, and the excess diethylenetriamine is distilled The temperature was lowered to 90°C to obtain 356.3 grams of tall oil acid imidazoline intermediate.
  • S.-F.Wang et al. used tall oil fatty acid and hydroxyethyl ethylenediamine as raw materials, and used xylene as a water-carrying agent to synthesize a tall oil acid imidazoline intermediate, which was then combined with 3-chloro-2-hydroxyl Sodium propanesulfonate synthesizes tall oil sulfonate.
  • the content of diamide by-product in the intermediate of tall oil acid imidazoline is too high, the product obtained has a darker color and poor stability, and xylene is used as a solvent, which is a type 3 carcinogenic solvent, which is not conducive to industrialization.
  • Quaternization Add 20ml of deionized water, 10.5g (0.03mol) of HEAI and 5.9g (0.03mol) of 3-chloro-2-hydroxypropanesulfonate into a three-necked flask, and heat to 80-90°C. While stirring, slowly add 10% aqueous sodium hydroxide (about 12 ml). Until the pH of the reaction mixture drops to 7-8. The synthesized mixture is then dried, and the water is pumped away under vacuum. Then dissolve the dried product with 50ml of absolute ethanol and filter to remove the undissolved NaCl. The filtrate is distilled to recover alcohol to obtain a light yellow transparent semi-solid.
  • the performance test of the tall oil fatty acid imidazoline sulfonate surfactant prepared in Examples 1-10 and Comparative Example 1 is shown in Table 1.
  • the biodegradability is based on the test of GB/T 15818-2006 Surfactant Biodegradability Method for testing (determined by foam method, degree of degradation on the seventh day.
  • the alkali resistance test is based on the corporate standard test: the surfactant is configured as a 10.0wt% aqueous solution, and 40.0wt% NaOH aqueous solution is slowly added to it, and the stirring is continued. Observe at any time. When the solution becomes turbid, stop adding immediately.
  • alkali resistance (1000 ⁇ m 2 )/m 3
  • Viscosity test conditions: temperature 25°C, speed: 20PRM, 64 rotor, Brookfield viscometer.
  • the conversion rate of intermediates is determined according to QB/T 2118-2012, the free amide content in the product is tested, and then determined by calculation.
  • Table 1 shows the performance of the tall oil fatty acid imidazoline sulfonate surfactant of the present invention
  • the alkali resistance of tall oil fatty acid imidazoline sulfonate surfactant is greater than 300gNaOH/L (the alkali resistance of lauric acid imidazoline is about 200gNaOH/L), the alkali resistance is better, and the solid content is The fluidity is good at 35%.
  • the tall oil fatty acid imidazoline sulfonate surfactant of the present invention is a new type of amphoteric surface agent, which has good decontamination, solubilization and emulsification, resistance to strong acids and alkalis, and excellent wax removal and corrosion inhibition effects , It has excellent emulsification and oil removal ability for mineral oils such as stamping oil, anti-rust oil and cutting oil. It is suitable for systems that require strong acid (60% sulfuric acid) and strong alkali (20% NaOH) and temperature resistance.
  • the synthetic route of the present invention is as follows:
  • R is specifically:
  • Trace amount of saturated fatty acid groups such as C16 acid alkyl part, C18 acid alkyl part, CH 3 (CH 2 ) 14 -CH 3 (CH 2 ) 16 -.
  • Figure 2 is the infrared spectra of tall oil fatty acid imidazoline sulfonate surfactants prepared in Example 11 of the present invention Spectrogram.
  • the structure is consistent, indicating that the tall oil fatty acid imidazoline sulfonate surfactant was successfully synthesized.
  • the cyclization reaction is at 220°C for 3h, the acid value is 1.8mgKOH/g after anhydrous distillation, the conversion rate of tall oil fatty acid (kraton FA2) is 98.9%, the vacuum is increased to 3mmhg, and the excess diethylenetriamine is distilled The temperature was lowered to 90°C to obtain 356.3 grams of tall oil acid imidazoline intermediate.
  • the temperature was raised to 70°C, and then (0.15 mol, 29.5 g) sodium 3-chloro-2-hydroxypropanesulfonate and (0.15 mol, 8.4 g) potassium hydroxide were added, reacted for 7 hours, and the chloride ion conversion rate was determined to be 99.5% ,
  • the conversion rate of the tall oil acid imidazoline intermediate is 92.5%, and the tall oil fatty acid imidazoline sulfonate surfactant is obtained with a solid content of 35%.
  • S.-F.Wang et al. used tall oil fatty acid and hydroxyethyl ethylenediamine as raw materials, and used xylene as a water-carrying agent to synthesize a tall oil acid imidazoline intermediate, which was then combined with 3-chloro-2-hydroxyl Sodium propanesulfonate synthesizes tall oil sulfonate.
  • the content of diamide by-product in the intermediate of tall oil acid imidazoline is too high, the product obtained has a darker color and poor stability, and xylene is used as a solvent, which is a type 3 carcinogenic solvent, which is not conducive to industrialization.
  • Quaternization Add 20ml of deionized water, 10.5g (0.03mol) of HEAI and 5.9g (0.03mol) of 3-chloro-2-hydroxypropanesulfonate into a three-necked flask, and heat to 80-90°C. While stirring, slowly add 10% aqueous sodium hydroxide (about 12 ml). Until the pH of the reaction mixture drops to 7-8. The synthesized mixture is then dried, and the water is pumped away under vacuum. Then use 50ml of absolute ethanol to dissolve the dried product, and filter to remove the undissolved NaCl. The filtrate is distilled to recover alcohol to obtain a light yellow transparent semi-solid.
  • the performance test of the tall oil fatty acid imidazoline sulfonate surfactant prepared in Examples 11-20 and Comparative Example 2 is shown in Table 2.
  • the degree of biodegradation is based on the test of GB/T 15818-2006 Surfactant Biodegradability Method for testing (determined by foam method, degree of degradation on the seventh day.
  • the alkali resistance test is based on the corporate standard test: the surfactant is configured as a 10.0wt% aqueous solution, and 40.0wt% NaOH aqueous solution is slowly added to it, and the stirring is continued. Observe at any time. When the solution becomes turbid, stop adding immediately.
  • alkali resistance (1000 ⁇ m 2 )/m 3
  • Viscosity test conditions: temperature 25°C, speed: 20PRM, 64 rotor, Brookfield viscometer.
  • the conversion rate of intermediates is determined according to QB/T 2118-2012, the free amide content in the product is tested, and then determined by calculation.
  • Table 2 is the performance of the tall oil fatty acid imidazoline sulfonate surfactant of the present invention
  • the alkali resistance of tall oil fatty acid imidazoline sulfonate surfactant is greater than 300gNaOH/L (the alkali resistance of lauric acid imidazoline is about 200gNaOH/L), the alkali resistance is better, and the solid content is The fluidity is good at 35%.
  • the tall oil fatty acid imidazoline sulfonate surfactant of the present invention is a new type of amphoteric surface agent, which has good decontamination, solubilization and emulsification, resistance to strong acids and alkalis, and excellent wax removal and corrosion inhibition effects , It has excellent emulsification and oil removal ability for mineral oils such as stamping oil, anti-rust oil and cutting oil. It is suitable for systems that require strong acid (60% sulfuric acid) and strong alkali (20% NaOH) and temperature resistance.

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Abstract

Disclosed is a tall oil fatty acid imidazoline sulfonate surfactant. A main component of the surfactant has a following structural formula: (I), wherein R is tall oil fatty acid alkyl. An intermediate of the tall oil fatty acid imidazoline sulfonate surfactant prepared by the present invention is low in diamide content, and the conversion rate of tall oil fatty acid is ≥ 98.5%. The product is low in stimulation, biodegradability is 100% in 7 days, the atom utilization rate is high, and alkali resistance and acid resistance are high. The surfactant has good appearance and stability, has excellent wax removal and corrosion inhibition effects, and has excellent emulsifying and oil stain stripping capabilities on mineral oils such as stamping oil, antirust oil, cutting oil and the like. A new route is provided for deep processing of tall oil products in China; the utilization rate of tall oil products can be greatly improved; the additional value of products can be improved; and notable economic benefits and social benefits can be achieved.

Description

一种妥尔油脂肪酸咪唑啉磺酸盐表面活性剂及制备方法Tall oil fatty acid imidazoline sulfonate surfactant and preparation method 技术领域Technical field
本发明属于表面活性剂技术领域，具体涉及一种妥尔油脂肪酸咪唑啉磺酸盐表面活性剂及制备方法。The invention belongs to the technical field of surfactants, and specifically relates to a tall oil fatty acid imidazoline sulfonate surfactant and a preparation method.
背景技术Background technique
妥尔油脂肪酸是由C 16、C 18链长的直链脂肪酸构成，主要成分为油酸、亚油酸等不饱和脂肪酸、少量饱和的棕榈酸、硬脂酸和松香酸构成，妥尔油脂肪酸来源十分丰富，是粗妥尔油通过蒸馏分离得到的，妥尔油(又称塔尔油、术浆浮油)是松木碱法制浆的副产物。目前，直接将妥尔油作为原材料的利用较少，其利用量约占粗妥尔油总量的10％，绝大多数粗妥尔油通过多级分离，然后再将这些原料制成其他产品。全球范围内，每年的妥尔油产量巨大。然而在我国，对妥尔油产品的深加工，并用于生产具有高附加值的表面活性剂和洗涤剂等方面的开发几乎是空白。在妥尔油中占有很大比例的脂肪酸成分正是表面活性剂工业的重要原料之一。 Tall oil fatty acids are composed of straight-chain fatty acids with C 16 and C 18 chain lengths. The main components are unsaturated fatty acids such as oleic acid and linoleic acid, and a small amount of saturated palmitic acid, stearic acid and rosin acid. Tall oil The source of fatty acids is very rich. It is obtained by distillation and separation of crude tall oil. Tall oil (also known as tall oil, tall oil) is a by-product of pine alkali pulping. At present, the use of tall oil directly as a raw material is rarely used, and its utilization accounts for about 10% of the total crude tall oil. The vast majority of crude tall oil is separated through multiple stages, and then these raw materials are made into other products. . Globally, the annual production of tall oil is huge. However, in our country, the development of the deep processing of tall oil products and the production of surfactants and detergents with high added value is almost blank. The fatty acid component, which occupies a large proportion in tall oil, is one of the important raw materials for the surfactant industry.
咪唑啉型表面活性剂是一种应用性能优良的表面活性剂，几乎与所有其他类型的表面活性剂配伍都会产生良好的协同效应，在日用化工、金属缓蚀、石油开采、纺织、印染等领域有着非常广阔的应用前景。如今，市面上销量最多的咪唑啉表面活性剂产品是月桂酸咪唑啉，含量一般为35％左右，巴斯夫、广州天赐、广州星业、上海发凯等均有销售，主要是由于所用的季铵化试剂易水解，产品粘度太大，影响传质效率，进一步影响咪唑啉中间体的转化率、产品稳定性和外观等。妥尔油脂肪酸主要由长碳链直链脂肪酸构成，用它合成的咪唑啉产品粘度会更大，而妥尔油脂肪酸成分的复杂性，也对产品工艺提出了很高的要求。Imidazoline surfactant is a surfactant with excellent application performance. It can produce good synergistic effects when compatible with almost all other types of surfactants. It can be used in daily chemical industry, metal corrosion inhibition, petroleum exploitation, textile, printing and dyeing, etc. The field has very broad application prospects. Today, the most sold imidazoline surfactant product on the market is imidazoline lauric acid with a content of about 35%. BASF, Guangzhou Tianci, Guangzhou Xingye, Shanghai Fakai, etc. are all sold, mainly due to the quaternary ammonium used The chemical reagent is easy to hydrolyze, and the product viscosity is too large, which affects the mass transfer efficiency, and further affects the conversion rate, product stability and appearance of the imidazoline intermediate. Tall oil fatty acids are mainly composed of long carbon chain straight chain fatty acids, and imidazoline products synthesized with it will have greater viscosity. The complexity of tall oil fatty acid composition also places high requirements on the product process.
表面活性剂在我国发展和更新速度较快，大宗表面活性剂的生产已完全满足国内需求，但多数技术水平要求较高、性能独特的绿色高效高值表面活性剂仍需大量进口。本发明针对市场对绿色可再生生物质原料表面活性剂的需求，以源自松木造纸行业副产物的妥尔油脂肪酸为原料，制备了一种妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，为我国妥尔油产品的深加工提供一条新的路线，可极大的提高妥尔油产品的利用率，提高产品附加值，具有显著的经济效益与社会效益。Surfactants are developing and renewing rapidly in my country. The production of bulk surfactants has fully met domestic demand, but most of the green, high-efficiency and high-value surfactants with high technical requirements and unique performance still need to be imported in large quantities. In response to the market’s demand for surfactants for green and renewable biomass raw materials, the present invention uses tall oil fatty acids derived from the by-products of the pine wood paper industry as raw materials to prepare a tall oil fatty acid imidazoline sulfonate surfactant. It provides a new route for the deep processing of tall oil products in our country, which can greatly improve the utilization rate of tall oil products, increase the added value of products, and have significant economic and social benefits.
如今妥尔油脂肪酸相关的应用一般是合成妥尔油酸酯类并应用在切削液中，这种产品是油溶性的，应用范围非常有限。专利CN104193774A用妥尔油脂肪酸、二乙醇胺和硼酸为 原料合成了一种妥尔油酸二乙酰胺硼酸酯，可直接稀释用于金属加工中的切削液，这种产品应用面非常狭小。S.-F.Wang等以妥尔油脂肪酸和羟乙基乙二胺为原料，用二甲苯做携水剂，合成了妥尔油酸咪唑啉中间体，再与3-氯-2-羟基丙磺酸钠合成妥尔油酸磺酸盐。妥尔油酸咪唑啉中间体中的二酰胺副产物含量太高，得到的产品色泽较深和稳定性较差，并且用二甲苯作溶剂，二甲苯是3类致癌溶剂，不利于工业化推广(S.-F.Wang,T.Furuno,Z.Cheng.Synthesis of 1-hydroxyethyl-2-alkyl-2-imidazoline and its derivative sulfonate amphoteric surfactant from tall oil fatty acid.J.Wood Sci.49(2003)371–376.)。Nowadays, the related application of tall oil fatty acids is generally to synthesize tall oil esters and apply them in cutting fluids. This product is oil-soluble and has a very limited range of applications. Patent CN104193774A uses tall oil fatty acid, diethanolamine and boric acid as raw materials to synthesize a tall oil acid diacetamide borate, which can directly dilute the cutting fluid used in metal processing. This product has a very narrow application range. S.-F.Wang et al. used tall oil fatty acid and hydroxyethyl ethylenediamine as raw materials, and used xylene as a water-carrying agent to synthesize a tall oil acid imidazoline intermediate, which was then combined with 3-chloro-2-hydroxyl Sodium propanesulfonate synthesizes tall oil sulfonate. The content of diamide by-product in the intermediate of tall oil acid imidazoline is too high, the product obtained has a darker color and poor stability, and xylene is used as a solvent, xylene is a type 3 carcinogenic solvent, which is not conducive to industrial promotion ( S.-F.Wang,T.Furuno,Z.Cheng.Synthesis of 1-hydroxyethyl-2-alkyl-2-imidazoline and its derivative sulfonate amhotericsurfactant from tall oil fatty acid.J.Wood Sci.49(2003)371 -376.).
发明内容Summary of the invention
针对妥尔油脂肪酸的成分复杂性、制备工艺控制要求较高、制备的咪唑啉粘度太大、影响传质效率和中间体的转化率等技术问题，本发明的目的在于提供一种妥尔油脂肪酸咪唑啉磺酸盐表面活性剂及制备方法。本发明针对市场对绿色可再生生物质原料表面活性剂的需求，对制浆造纸行业的副产物-妥尔油脂肪酸资源进行深加工，资源再利用，制备了一种妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，改善了产品的粘度，这种表面活性剂低刺激，7天生物降解性为100％，原子利用率高，高耐碱性、外观和稳定性较好。In view of the complex composition of tall oil fatty acids, high requirements for preparation process control, high viscosity of the prepared imidazoline, influence on mass transfer efficiency and intermediate conversion rate and other technical problems, the purpose of the present invention is to provide a tall oil Fatty acid imidazoline sulfonate surfactant and preparation method. In response to the market’s demand for surfactants for green and renewable biomass raw materials, the invention deep-processes tall oil fatty acid resources, a by-product of the pulp and paper industry, and reuses the resources to prepare a tall oil fatty acid imidazoline sulfonic acid The salt surfactant improves the viscosity of the product. This surfactant has low irritation, 100% biodegradability in 7 days, high atom utilization, high alkali resistance, good appearance and stability.
为了实现上述目的，本发明采用的技术方案如下：In order to achieve the above objectives, the technical solutions adopted by the present invention are as follows:
本发明的第一个方面提供了一种妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，其主要成分结构式如下：The first aspect of the present invention provides a tall oil fatty acid imidazoline sulfonate surfactant, the main component structural formula of which is as follows:
Figure PCTCN2020114502-appb-000001
Figure PCTCN2020114502-appb-000001
其中，R为妥尔油脂肪酸烷基。Among them, R is a tall oil fatty acid alkyl group.
所述妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备原料采用市售的妥尔油脂肪酸，市售的妥尔油脂肪酸的主要成分为油酸、亚油酸、松香酸和少量饱和脂肪酸，R主要为对应的油酸、亚油酸烷基基团、松香酸烷基基团、饱和脂肪酸基团；The tall oil fatty acid imidazoline sulfonate surfactant is prepared as a raw material using commercially available tall oil fatty acids, and the main components of the commercially available tall oil fatty acids are oleic acid, linoleic acid, abietic acid and a small amount of saturated fatty acids , R is mainly the corresponding oleic acid, linoleic acid alkyl group, rosin acid alkyl group, saturated fatty acid group;
油酸烷基基团：CH 3(CH 2) 7CH＝CH(CH 2) 7 - Oleic alkyl group: CH 3 (CH 2) 7 CH = CH (CH 2) 7 -
亚油酸烷基基团：CH 3(CH 2) 4CH＝CHCH 2CH＝CH(CH 2) 7 - Linoleic alkyl group: CH 3 (CH 2) 4 CH = CHCH 2 CH = CH (CH 2) 7 -
松香酸烷基基团：
Figure PCTCN2020114502-appb-000002
Rosin acid alkyl group:
Figure PCTCN2020114502-appb-000002
微量的饱和脂肪酸基团：如C16酸烷基部分、C18酸烷基部分， CH 3(CH 2) 14-CH 3(CH 2) 16-。 Trace amount of saturated fatty acid groups: such as C16 acid alkyl part, C18 acid alkyl part, CH 3 (CH 2 ) 14 -CH 3 (CH 2 ) 16 -.
本发明的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂含有所述主要成分、水以及制备过程中不可避免的副产物，其固含量为30-40％，优选为35％。The tall oil fatty acid imidazoline sulfonate surfactant of the present invention contains the main components, water and by-products unavoidable in the preparation process, and its solid content is 30-40%, preferably 35%.
本发明的第二个方面提供了一种所述妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，包括以下步骤：The second aspect of the present invention provides a preparation method of the tall oil fatty acid imidazoline sulfonate surfactant, which comprises the following steps:
第一步，妥尔油酸咪唑啉中间体的合成：The first step is the synthesis of tall oil acid imidazoline intermediates:
在氮气保护下，将妥尔油脂肪酸、有机多胺混合，加入磷酸作为催化剂，所述妥尔油脂肪酸、有机多胺、磷酸的摩尔比为1:(0.5～2):(0.005～0.05)，调节反应体系真空残压至20～300mmhg，然后梯度升温反应，直至无水蒸出为止，测量酸值，调整真空，蒸馏出过量的原料，降温，获得所述妥尔油酸咪唑啉中间体；Under the protection of nitrogen, the tall oil fatty acid and organic polyamine are mixed, and phosphoric acid is added as a catalyst. The molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1:(0.5-2):(0.005-0.05) , Adjust the vacuum residual pressure of the reaction system to 20-300mmhg, and then react with gradient heating until the anhydrous is evaporated, measure the acid value, adjust the vacuum, distill out excess raw materials, and cool down to obtain the tall oil acid imidazoline intermediate ；
第二步，季铵化反应：将第一步获得的妥尔油酸咪唑啉中间体、碱、去离子水混合，妥尔油酸咪唑啉中间体、碱、去离子水的质量比为1:(0.1～0.4):(2～10)，温度为40～100℃(优选为60～90℃)的条件下与烷基磺酸钠反应，所述妥尔油酸咪唑啉中间体和烷基磺酸钠的摩尔比为1:(1～3)，反应至氯离子含量不再变化，得到所述妥尔油脂肪酸咪唑啉磺酸盐表面活性剂。The second step is the quaternization reaction: the tall oil acid imidazoline intermediate obtained in the first step, alkali, and deionized water are mixed, and the mass ratio of tall oil imidazoline intermediate, alkali, and deionized water is 1 :(0.1～0.4):(2～10), react with sodium alkyl sulfonate at a temperature of 40～100℃ (preferably 60～90℃), the tall oil acid imidazoline intermediate and alkane The molar ratio of sodium base sulfonate is 1: (1 to 3), and the reaction is performed until the chloride ion content no longer changes to obtain the tall oil fatty acid imidazoline sulfonate surfactant.
所述有机多胺为羟乙基乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中的至少一种，优选为羟乙基乙二胺、二乙烯三胺。The organic polyamine is at least one of hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, preferably hydroxyethylethylenediamine and diethylenetriamine.
所述妥尔油脂肪酸、有机多胺、磷酸的摩尔比为1:(1.1～1.5):(0.005～0.01)。The molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1: (1.1 to 1.5): (0.005 to 0.01).
所述梯度升温反应是指从室温升温至90～110℃，以5～25℃/h升温速率梯度升温至160～180℃反应1～48h，升温至210～250℃环化反应1～48h。The gradient heating reaction refers to heating from room temperature to 90-110°C, heating to 160-180°C at a heating rate of 5-25°C/h for 1 to 48 hours, and heating to 210-250°C for cyclization reaction for 1 to 48 hours.
所述酸值为中间体酸值小于3mgKOH/g。The acid value of the intermediate acid value is less than 3 mgKOH/g.
所述调整真空为2～3mmhg。The adjusted vacuum is 2 to 3 mmhg.
所述降温是指温度为80～100℃，优选为90℃。The cooling means that the temperature is 80-100°C, preferably 90°C.
所述碱为NaOH、KOH或Na 2CO 3。 The base is NaOH, KOH or Na 2 CO 3 .
所述妥尔油酸咪唑啉中间体、碱、去离子水的质量比为1:(0.1～0.4):(3～5)。The mass ratio of the tall oil acid imidazoline intermediate, alkali, and deionized water is 1:(0.1-0.4):(3-5).
所述妥尔油酸咪唑啉中间体和烷基磺酸钠的摩尔比为1:(1.1～2)。The molar ratio of the tall oil acid imidazoline intermediate and the sodium alkyl sulfonate is 1: (1.1-2).
所述烷基磺酸钠为3-氯-2-羟基丙磺酸钠、2-溴乙基磺酸钠、2-氯乙基磺酸钠、烯丙基磺酸钠，优选为3-氯-2-羟基丙磺酸钠。The sodium alkyl sulfonate is sodium 3-chloro-2-hydroxypropane sulfonate, sodium 2-bromoethyl sulfonate, sodium 2-chloroethyl sulfonate, sodium allyl sulfonate, preferably 3-chloro Sodium-2-hydroxypropanesulfonate.
本发明的第三个方面提供了一种所述妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，包括以下步骤：The third aspect of the present invention provides a method for preparing the tall oil fatty acid imidazoline sulfonate surfactant, which includes the following steps:
第一步，妥尔油酸咪唑啉中间体的合成：The first step is the synthesis of tall oil acid imidazoline intermediates:
在氮气保护下，将妥尔油脂肪酸、有机多胺混合，加入磷酸作为催化剂，所述妥尔油脂肪酸、有机多胺、磷酸的摩尔比为1:(0.5～2):(0.005～0.05)，调节反应体系真空残压至20～300mmhg，然后梯度升温反应，直至无水蒸出为止，测量酸值，调整真空，蒸馏出过量的原料，降温，获得所述妥尔油酸咪唑啉中间体；Under the protection of nitrogen, the tall oil fatty acid and organic polyamine are mixed, and phosphoric acid is added as a catalyst. The molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1:(0.5-2):(0.005-0.05) , Adjust the vacuum residual pressure of the reaction system to 20-300mmhg, and then react with gradient heating until the anhydrous is evaporated, measure the acid value, adjust the vacuum, distill out excess raw materials, and cool down to obtain the tall oil acid imidazoline intermediate ；
第二步，季铵化反应：将第一步获得的妥尔油酸咪唑啉中间体、低碳醇、碱、去离子水混合，妥尔油酸咪唑啉中间体、低碳醇、碱、去离子水的质量比为1:(0.01～1):(0.1～0.4):(2～10)，温度为40～100℃(优选为60～90℃)的条件下与烷基磺酸钠反应，所述妥尔油酸咪唑啉中间体和烷基磺酸钠的摩尔比为1:(1～3)，反应至氯离子含量不再变化，得到所述妥尔油脂肪酸咪唑啉磺酸盐表面活性剂。The second step is the quaternization reaction: the tall oil acid imidazoline intermediate obtained in the first step, lower alcohol, alkali, and deionized water are mixed, tall oil acid imidazoline intermediate, lower alcohol, alkali, The mass ratio of deionized water is 1:(0.01～1):(0.1～0.4):(2～10), and the temperature is 40～100℃ (preferably 60～90℃) with sodium alkyl sulfonate In the reaction, the molar ratio of the tall oil acid imidazoline intermediate and the sodium alkyl sulfonate is 1: (1 to 3), and the reaction is performed until the chloride ion content no longer changes to obtain the tall oil fatty acid imidazoline sulfonic acid Salt surfactants.
所述有机多胺为羟乙基乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中的至少一种，优选为羟乙基乙二胺、二乙烯三胺。The organic polyamine is at least one of hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, preferably hydroxyethylethylenediamine and diethylenetriamine.
所述妥尔油脂肪酸、有机多胺、磷酸的摩尔比为1:(1.1～1.5):(0.005～0.01)。The molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1: (1.1 to 1.5): (0.005 to 0.01).
所述梯度升温反应是指从室温升温至90～110℃，以5～25℃/h升温速率梯度升温至160～180℃反应1～48h，升温至210～250℃环化反应1～48h。The gradient heating reaction refers to heating from room temperature to 90-110°C, heating to 160-180°C at a heating rate of 5-25°C/h for 1 to 48 hours, and heating to 210-250°C for cyclization reaction for 1 to 48 hours.
所述酸值为中间体酸值小于3mgKOH/g。The acid value of the intermediate acid value is less than 3 mgKOH/g.
所述调整真空为2～3mmhg。The adjusted vacuum is 2 to 3 mmhg.
所述降温是指温度为80～100℃，优选为90℃。The cooling means that the temperature is 80-100°C, preferably 90°C.
所述低碳醇为甲醇、乙醇、异丙醇或乙二醇，优选乙醇、异丙醇。The lower alcohol is methanol, ethanol, isopropanol or ethylene glycol, preferably ethanol or isopropanol.
所述碱为NaOH、KOH或Na 2CO 3。 The base is NaOH, KOH or Na 2 CO 3 .
所述妥尔油酸咪唑啉中间体、低碳醇、碱、去离子水的质量比为1:(0.4～0.6):(0.1～0.4):(2.5～4)。The mass ratio of the tall oil acid imidazoline intermediate, lower alcohol, alkali, and deionized water is 1:(0.4~0.6):(0.1~0.4):(2.5~4).
所述烷基磺酸钠为3-氯-2-羟基丙磺酸钠、2-溴乙基磺酸钠、2-氯乙基磺酸钠、烯丙基磺酸钠，优选为3-氯-2-羟基丙磺酸钠。The sodium alkyl sulfonate is sodium 3-chloro-2-hydroxypropane sulfonate, sodium 2-bromoethyl sulfonate, sodium 2-chloroethyl sulfonate, sodium allyl sulfonate, preferably 3-chloro Sodium-2-hydroxypropanesulfonate.
所述妥尔油酸咪唑啉中间体和烷基磺酸钠的摩尔比为1:(1.1～2)。The molar ratio of the tall oil acid imidazoline intermediate and the sodium alkyl sulfonate is 1: (1.1-2).
由于采用上述技术方案，本发明具有以下优点和有益效果：Due to the adoption of the above technical solutions, the present invention has the following advantages and beneficial effects:
本发明制备的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂中间体二酰胺含量少，妥尔油脂肪酸(kraton FA2)转化率≥98.5％，产品低刺激，7天生物降解性为100％，原子利用率高，高耐碱耐酸性，外观和稳定性较好，有着优异的除蜡和缓蚀效果，对冲压油、防锈油和切削油等矿物油有着优异的乳化和油污剥离能力，为我国妥尔油产品的深加工提供一条新的路线，可极大的提高妥尔油产品的利用率，提高产品附加值，具有显著的经济效益与社会效益。The tall oil fatty acid imidazoline sulfonate surfactant intermediate prepared by the present invention has a low content of diamide, a tall oil fatty acid (kraton FA2) conversion rate of ≥98.5%, low product irritation, and a 7-day biodegradability of 100%. High atom utilization, high alkali and acid resistance, good appearance and stability, excellent wax removal and corrosion inhibition effects, excellent emulsification and oil removal ability for mineral oils such as stamping oil, rust preventive oil and cutting oil. The deep processing of tall oil products in our country provides a new route, which can greatly improve the utilization rate of tall oil products, increase the added value of products, and have significant economic and social benefits.
本发明的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法中，梯度升温是为了更好的 节省能耗，避免温度过高，反应太快，产生更多的副产物。In the preparation method of the tall oil fatty acid imidazoline sulfonate surfactant of the present invention, the gradient temperature increase is to better save energy consumption, avoid excessively high temperature, too fast reaction, and produce more by-products.
本发明以妥尔油脂肪酸为原料，通过中间体测控技术实现复杂原料的中间体选择性调控，并用水为溶剂进行季铵化反应，获得妥尔油脂肪酸咪唑啉磺酸盐表面活性剂。The invention uses tall oil fatty acid as a raw material, realizes the selective control of intermediates of complex raw materials through intermediate measurement and control technology, and performs quaternization reaction with water as a solvent to obtain a tall oil fatty acid imidazoline sulfonate surfactant.
本发明以妥尔油脂肪酸为原料，通过中间体测控技术实现复杂原料的中间体选择性调控，并用少量低碳醇和水为溶剂进行季铵化反应，获得妥尔油脂肪酸咪唑啉磺酸盐表面活性剂。The invention uses tall oil fatty acid as raw material, realizes the selective regulation of complex raw material intermediates through intermediate measurement and control technology, and uses a small amount of lower alcohol and water as solvents for quaternization to obtain the surface of tall oil fatty acid imidazoline sulfonate. Active agent.
附图说明Description of the drawings
图1为本发明实施例1制备的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的红外谱图。Figure 1 is an infrared spectrum of the tall oil fatty acid imidazoline sulfonate surfactant prepared in Example 1 of the present invention.
图2为本发明实施例11制备的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的红外谱图。Figure 2 is an infrared spectrum of the tall oil fatty acid imidazoline sulfonate surfactant prepared in Example 11 of the present invention.
具体实施方式detailed description
为了更清楚地说明本发明，下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。In order to illustrate the present invention more clearly, the following further describes the present invention in combination with preferred embodiments. Those skilled in the art should understand that the content described below is illustrative rather than restrictive, and should not be used to limit the protection scope of the present invention.
本发明所用试剂妥尔油脂肪酸(kraton FA2)，工业级，纯度没有标准，COA酸值：196，松香酸含量：0.8％，不皂化物：1.3，碘值：125，色泽，Gardner：3，购买厂家：无锡恒懋科贸有限公司。The reagent used in the present invention is tall oil fatty acid (kraton FA2), technical grade, purity is not standard, COA acid value: 196, rosin acid content: 0.8%, unsaponifiable matter: 1.3, iodine value: 125, color, Gardner: 3, Purchase manufacturer: Wuxi Hengmao Technology & Trade Co., Ltd.
本发明实施例制备的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，其主要成分结构式如下：The structural formula of main components of the tall oil fatty acid imidazoline sulfonate surfactant prepared in the embodiment of the present invention is as follows:
Figure PCTCN2020114502-appb-000003
Figure PCTCN2020114502-appb-000003
其中，R为妥尔油脂肪酸烷基。Among them, R is a tall oil fatty acid alkyl group.
R主要为对应的油酸、亚油酸烷基基团、松香酸烷基基团、饱和脂肪酸基团；R is mainly the corresponding oleic acid, linoleic acid alkyl group, rosin acid alkyl group, and saturated fatty acid group;
油酸烷基基团：CH 3(CH 2) 7CH＝CH(CH 2) 7 - Oleic alkyl group: CH 3 (CH 2) 7 CH = CH (CH 2) 7 -
亚油酸烷基基团：CH 3(CH 2) 4CH＝CHCH 2CH＝CH(CH 2) 7 - Linoleic alkyl group: CH 3 (CH 2) 4 CH = CHCH 2 CH = CH (CH 2) 7 -
松香酸烷基基团：
Figure PCTCN2020114502-appb-000004
Rosin acid alkyl group:
Figure PCTCN2020114502-appb-000004
微量的饱和脂肪酸基团：如C16酸烷基部分、C18酸烷基部分，CH 3(CH 2) 14-CH 3(CH 2) 16-。 Trace amount of saturated fatty acid groups: such as C16 acid alkyl part, C18 acid alkyl part, CH 3 (CH 2 ) 14 -CH 3 (CH 2 ) 16 -.
实施例1Example 1
以羟乙基乙二胺为例，本发明的合成路线如下：Taking hydroxyethyl ethylene diamine as an example, the synthetic route of the present invention is as follows:
Figure PCTCN2020114502-appb-000005
Figure PCTCN2020114502-appb-000005
其中，R具体是：Among them, R is specifically:
油酸烷基基团：CH 3(CH 2) 7CH＝CH(CH 2) 7 - Oleic alkyl group: CH 3 (CH 2) 7 CH = CH (CH 2) 7 -
亚油酸烷基基团：CH 3(CH 2) 4CH＝CHCH 2CH＝CH(CH 2) 7 - Linoleic alkyl group: CH 3 (CH 2) 4 CH = CHCH 2 CH = CH (CH 2) 7 -
松香酸烷基基团：
Figure PCTCN2020114502-appb-000006
Rosin acid alkyl group:
Figure PCTCN2020114502-appb-000006
微量的饱和脂肪酸基团：如C16酸烷基部分、C18酸烷基部分，CH 3(CH 2) 14-CH 3(CH 2) 16-。 Trace amount of saturated fatty acid groups: such as C16 acid alkyl part, C18 acid alkyl part, CH 3 (CH 2 ) 14 -CH 3 (CH 2 ) 16 -.
在装有电动搅拌器、温度计、氮气导入管及减压蒸馏装置的1升四口烧瓶中，加入(1.5摩尔、156.3克)羟乙基乙二胺，在搅拌和氮气保护条件下加入(1摩尔、286.2克)妥尔油脂肪酸(kraton FA2)和0.9克磷酸，开动真空泵调节反应体系真空残压至150mmhg，升温至100℃开始计时，以20℃/h升温速率梯度升温至170℃反应2h，升温至220℃环化反应2h，无水蒸出后测酸值为2.4mgKOH/g，妥尔油脂肪酸(kraton FA2)转化率为98.5％，把真空提高至2mmhg，把过量的羟乙基乙二胺蒸馏出，降温至90℃，得到妥尔油酸咪唑啉中间体355.3克，二酰胺含量为2.5％。In a 1-liter four-necked flask equipped with an electric stirrer, a thermometer, a nitrogen introduction tube and a vacuum distillation device, add (1.5 moles, 156.3 g) hydroxyethyl ethylene diamine, add (1 Mol, 286.2g) tall oil fatty acid (kraton FA2) and 0.9g phosphoric acid, turn on the vacuum pump to adjust the vacuum residual pressure of the reaction system to 150mmhg, start timing when the temperature is raised to 100°C, and increase the temperature to 170°C at a heating rate of 20°C/h for 2h , The temperature was raised to 220°C for cyclization reaction for 2h, the acid value measured after anhydrous steaming was 2.4mgKOH/g, the conversion rate of tall oil fatty acid (kraton FA2) was 98.5%, the vacuum was increased to 2mmhg, and the excess hydroxyethyl Ethylenediamine was distilled out, and the temperature was lowered to 90°C to obtain 355.3 g of a tall oil acid imidazoline intermediate with a diamide content of 2.5%.
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)上述妥尔油酸咪唑啉中间体、153.6克去离子水和(0.2摩尔、8克)氢氧化钠，升温至90℃，再加入(0.2摩尔、39.3克)3-氯-2-羟基丙磺酸钠，反应5h，测得氯离子转化率为99.7％，妥尔油酸咪唑啉中间体转化率为92.3％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, thermometer and condenser, add (0.1 mole, 35.4 g) the tall oil acid imidazoline intermediate, 153.6 g deionized water and (0.2 mole, 8 g) hydrogen Sodium oxide, heated to 90°C, then added (0.2 mol, 39.3 g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 5 hours, the measured chloride ion conversion rate was 99.7%, tall oil acid imidazoline intermediate The conversion rate was 92.3%, and a tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
妥尔油脂肪酸和妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的红外光谱如图1所示，图1为本发明实施例1制备的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的红外谱图。其中2923cm -1附近为C-H的振动吸收峰；2852cm -1附近为C-N的振动吸收峰；2853cm -1处附近为CH 2中 C-H键的对称伸缩振动；1708cm -1处的吸收峰为COOH上的羰基振动峰；1625cm -1附近的吸收峰为C＝O特征吸收峰；说明季铵化反应时妥尔油酸咪唑啉环水解；1190cm -1为磺酸基的特征吸收峰，官能团特征与产物结构相符，表明成功合成了妥尔油脂肪酸咪唑啉磺酸盐表面活性剂。 The infrared spectra of tall oil fatty acid and tall oil fatty acid imidazoline sulfonate surfactants are shown in Figure 1. Figure 1 is the infrared spectra of tall oil fatty acid imidazoline sulfonate surfactants prepared in Example 1 of the present invention Spectrogram. Among them, near 2923cm -1 is the vibration absorption peak of CH; near 2852cm -1 is the vibration absorption peak of CN; near 2853cm -1 is the symmetric stretching vibration of the CH bond in CH 2 ; the absorption peak at 1708 cm -1 is on COOH The carbonyl vibration peak; the absorption peak near 1625 cm -1 is the characteristic absorption peak of C=O; it shows that the tall oil acid imidazoline ring is hydrolyzed during the quaternization reaction; 1190 cm -1 is the characteristic absorption peak of the sulfonic acid group, the characteristics of the functional group and the product The structure is consistent, indicating that the tall oil fatty acid imidazoline sulfonate surfactant was successfully synthesized.
实施例2Example 2
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例1制备得到的妥尔油酸咪唑啉中间体、131.7克去离子水和(0.15摩尔、6克)氢氧化钠，升温至80℃，再加入(0.15摩尔、29.5克)3-氯-2-羟基丙磺酸钠，反应6h，测得氯离子转化率为99.5％，妥尔油酸咪唑啉中间体转化率为93.2％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-neck flask equipped with an electric stirrer, thermometer and condenser, add (0.1 mole, 35.4 g) the tall oil imidazoline intermediate prepared in Example 1, 131.7 g deionized water and (0.15 mole , 6g) sodium hydroxide, heated to 80°C, then added (0.15 mole, 29.5g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 6h, the measured chloride ion conversion rate was 99.5%, tall oil The conversion rate of the acid imidazoline intermediate is 93.2%, and the tall oil fatty acid imidazoline sulfonate surfactant is obtained with a solid content of 35%.
实施例3Example 3
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例1制备得到的妥尔油酸咪唑啉中间体、114.1克去离子水和(0.15摩尔、6克)氢氧化钠，升温至70℃，再加入(0.11摩尔、21.6克)3-氯-2-羟基丙磺酸钠，反应7h，测得氯离子转化率为99.6％，妥尔油酸咪唑啉中间体转化率为92.0％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, thermometer and condenser, add (0.1 mole, 35.4 g) the tall oil imidazoline intermediate prepared in Example 1, 114.1 g deionized water and (0.15 mole , 6g) sodium hydroxide, heated to 70℃, then added (0.11mol, 21.6g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 7h, the conversion rate of chloride ion was measured to be 99.6%, tall oil The conversion rate of the acid imidazoline intermediate was 92.0%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例4Example 4
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例1制备得到的妥尔油酸咪唑啉中间体、136.2克去离子水和(0.15摩尔、8.4克)氢氧化钾，升温至80℃，再加入(0.15摩尔、29.5克)3-氯-2-羟基丙磺酸钠，反应6h，测得氯离子转化率为99.2％，妥尔油酸咪唑啉中间体转化率为93.1％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-neck flask equipped with an electric stirrer, thermometer and condenser, add (0.1 mole, 35.4 g) the tall oil imidazoline intermediate prepared in Example 1, 136.2 g deionized water and (0.15 mole 8.4 g) potassium hydroxide, heated to 80°C, then added (0.15 mol, 29.5 g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 6 hours, the conversion rate of chloride ion was measured to be 99.2%, tall oil The conversion rate of the acid imidazoline intermediate was 93.1%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例5Example 5
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例1制备得到的妥尔油酸咪唑啉中间体、159.7克去离子水和(0.2摩尔、11.2克)氢氧化钾，升温至70℃，再加入(0.2摩尔、39.3克)3-氯-2-羟基丙磺酸钠，反应7h，测得氯离子转化率为99.3％，妥尔油酸咪唑啉中间体转化率为94.5％，得到妥尔油脂肪酸咪唑啉磺酸盐 表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, add (0.1 mole, 35.4 g) the tall oil imidazoline intermediate prepared in Example 1, 159.7 g deionized water and (0.2 mole , 11.2g) potassium hydroxide, heated to 70℃, then added (0.2mol, 39.3g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 7h, the conversion rate of chloride ion was measured to be 99.3%, tall oil The conversion rate of the acid imidazoline intermediate was 94.5%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例6Example 6
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例1制备得到的妥尔油酸咪唑啉中间体、117.5克去离子水和(0.11摩尔、6.2克)氢氧化钾，升温至60℃，再加入(0.11摩尔、21.6克)3-氯-2-羟基丙磺酸钠，反应8h，测得氯离子转化率为99.2％，妥尔油酸咪唑啉中间体转化率为90.0％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, add (0.1 mole, 35.4 g) the tall oil acid imidazoline intermediate prepared in Example 1, 117.5 g deionized water and (0.11 mole , 6.2g) potassium hydroxide, heated to 60℃, then added (0.11mol, 21.6g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 8h, the chloride ion conversion rate was 99.2%, tall oil The conversion rate of the acid imidazoline intermediate is 90.0%, and the tall oil fatty acid imidazoline sulfonate surfactant is obtained with a solid content of 35%.
实施例7Example 7
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例1制备得到的妥尔油酸咪唑啉中间体、158.2克去离子水和(0.1摩尔、10.6克)碳酸钠，升温至90℃，再加入(0.2摩尔、39.3克)3-氯-2-羟基丙磺酸钠，反应6h，测得氯离子转化率为98.8％，妥尔油酸咪唑啉中间体转化率为92.1％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, add (0.1 mole, 35.4 g) the tall oil imidazoline intermediate prepared in Example 1, 158.2 g deionized water and (0.1 mole , 10.6g) sodium carbonate, heated to 90°C, then added (0.2mol, 39.3g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 6h, the measured chloride ion conversion rate was 98.8%, tall oil acid The conversion rate of the imidazoline intermediate was 92.1%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例8Example 8
在装有电动搅拌器、温度计、氮气导入管及减压蒸馏装置的1升四口烧瓶中，加入(1.2摩尔、123.8克)二乙烯三胺，在搅拌和氮气保护条件下加入(1摩尔、286.2克)妥尔油脂肪酸(kraton FA2)和0.8克磷酸，开动真空泵调节反应体系真空残压至180mmhg，升温至100℃开始计时，以20℃/h升温速率梯度升温至170℃反应2h，升温至220℃环化反应3h，无水蒸出后测酸值为1.8mgKOH/g，妥尔油脂肪酸(kraton FA2)转化率为98.9％，把真空提高至3mmhg，把过量的二乙烯三胺蒸馏出，降温至90℃，得到妥尔油酸咪唑啉中间体356.3克。In a 1-liter four-necked flask equipped with an electric stirrer, a thermometer, a nitrogen introduction tube and a vacuum distillation device, add (1.2 moles, 123.8 g) diethylene triamine, add (1 mole, 286.2g) tall oil fatty acid (kraton FA2) and 0.8g phosphoric acid, turn on the vacuum pump to adjust the vacuum residual pressure of the reaction system to 180mmhg, start timing when the temperature is raised to 100°C, and react with a gradient of 20°C/h to 170°C and react for 2h. The cyclization reaction is at 220℃ for 3h, the acid value is 1.8mgKOH/g after anhydrous distillation, the conversion rate of tall oil fatty acid (kraton FA2) is 98.9%, the vacuum is increased to 3mmhg, and the excess diethylenetriamine is distilled The temperature was lowered to 90°C to obtain 356.3 grams of tall oil acid imidazoline intermediate.
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.3克)上述妥尔油酸咪唑啉中间体、153.3克去离子水和(0.2摩尔、8克)氢氧化钠，升温至80℃，再加入(0.2摩尔、39.3克)3-氯-2-羟基丙磺酸钠，反应6h，测得氯离子转化率为99.5％，妥尔油酸咪唑啉中间体转化率为91.6％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, thermometer and condenser, add (0.1 mole, 35.3 g) the tall oil acid imidazoline intermediate, 153.3 g deionized water and (0.2 mole, 8 g) hydrogen Sodium oxide, heated to 80°C, then added (0.2 mol, 39.3 g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 6 hours, the measured chloride ion conversion rate was 99.5%, tall oil acid imidazoline intermediate The conversion rate was 91.6%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例9Example 9
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.3克)实施例8制备得到的妥尔油酸咪唑啉中间体、135.9克去离子水，升温至70℃，再加入(0.15摩尔、29.5克)3-氯-2-羟基丙磺酸钠和(0.15摩尔、8.4克)氢氧化钾，反应7h，测得氯离子转化率为99.3％，妥尔油酸咪唑啉中间体转化率为92.3％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, add (0.1 mole, 35.3 g) the tall oil imidazoline intermediate prepared in Example 8 and 135.9 g of deionized water, and heat to 70 ℃, add (0.15 mol, 29.5 g) sodium 3-chloro-2-hydroxypropanesulfonate and (0.15 mol, 8.4 g) potassium hydroxide, react for 7 hours, the chloride ion conversion rate is 99.3%, tall oil The conversion rate of the acid imidazoline intermediate was 92.3%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例10Example 10
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.3克)实施例8制备得到的妥尔油酸咪唑啉中间体、158.2克去离子水和(0.1摩尔、10.6克)碳酸钠，升温至90℃，再加入(0.2摩尔、39.3克)3-氯-2-羟基丙磺酸钠，反应6h，测得氯离子转化率为98.7％，妥尔油酸咪唑啉中间体转化率为89.9％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, add (0.1 mole, 35.3 g) the tall oil imidazoline intermediate prepared in Example 8, 158.2 g deionized water and (0.1 mole , 10.6g) sodium carbonate, heated to 90°C, then added (0.2mol, 39.3g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 6h, the measured chloride ion conversion rate was 98.7%, tall oil acid The conversion rate of the imidazoline intermediate was 89.9%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
对比例1Comparative example 1
S.-F.Wang等以妥尔油脂肪酸和羟乙基乙二胺为原料，用二甲苯做携水剂，合成了妥尔油酸咪唑啉中间体，再与3-氯-2-羟基丙磺酸钠合成妥尔油酸磺酸盐。妥尔油酸咪唑啉中间体中的二酰胺副产物含量太高，得到的产品色泽较深和稳定性较差，并且用二甲苯作溶剂，二甲苯是3类致癌溶剂，不利于工业化推广。S.-F.Wang et al. used tall oil fatty acid and hydroxyethyl ethylenediamine as raw materials, and used xylene as a water-carrying agent to synthesize a tall oil acid imidazoline intermediate, which was then combined with 3-chloro-2-hydroxyl Sodium propanesulfonate synthesizes tall oil sulfonate. The content of diamide by-product in the intermediate of tall oil acid imidazoline is too high, the product obtained has a darker color and poor stability, and xylene is used as a solvent, which is a type 3 carcinogenic solvent, which is not conducive to industrialization.
制备方法：中间体HEAI合成：装有搅拌器、回流冷凝器、分水器和温度计的四口烧瓶加入56.4g(0.2mol)妥尔油脂肪酸，0.2mol羟乙基乙二胺和100毫升二甲苯。反应物在140-150℃回流至没有更多的水从分水器流出。拆除分水器，将反应体系压力调整到14.66kPa，反应温度提高到250℃，反应30min，得到半固体的妥尔油咪唑啉中间体HEAI，二酰胺含量：4.1％。Preparation method: Intermediate HEAI synthesis: a four-necked flask equipped with a stirrer, reflux condenser, water separator and thermometer was added 56.4g (0.2mol) tall oil fatty acid, 0.2mol hydroxyethylethylenediamine and 100ml diamine Toluene. The reactants are refluxed at 140-150°C until no more water flows out of the trap. Remove the water trap, adjust the pressure of the reaction system to 14.66kPa, increase the reaction temperature to 250°C, and react for 30 minutes to obtain the semi-solid tall oil imidazoline intermediate HEAI with a diamide content: 4.1%.
季铵化：三口烧瓶中加入去离子水20ml，10.5g(0.03mol)的HEAI以及5.9g(0.03mol)3-氯-2-羟基丙磺酸盐，加热至80-90℃。在搅拌下，缓慢加入10％水溶液氢氧化钠(约12ml)。直到反应混合物的pH值下降到7-8。然后对合成的混合物进行干燥，在真空状态下，把水抽走。再用50ml无水乙醇溶解干燥产物，过滤除去未溶解的NaCl。滤液经蒸馏回收酒精，得到淡黄色透明半固体。Quaternization: Add 20ml of deionized water, 10.5g (0.03mol) of HEAI and 5.9g (0.03mol) of 3-chloro-2-hydroxypropanesulfonate into a three-necked flask, and heat to 80-90°C. While stirring, slowly add 10% aqueous sodium hydroxide (about 12 ml). Until the pH of the reaction mixture drops to 7-8. The synthesized mixture is then dried, and the water is pumped away under vacuum. Then dissolve the dried product with 50ml of absolute ethanol and filter to remove the undissolved NaCl. The filtrate is distilled to recover alcohol to obtain a light yellow transparent semi-solid.
实施例1～10及对比例1制备的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的性能测试如表1所示，生物降解度根据GB/T 15818-2006表面活性剂生物降解度的试验方法进行测试(泡沫法测定，第七天的降解度。The performance test of the tall oil fatty acid imidazoline sulfonate surfactant prepared in Examples 1-10 and Comparative Example 1 is shown in Table 1. The biodegradability is based on the test of GB/T 15818-2006 Surfactant Biodegradability Method for testing (determined by foam method, degree of degradation on the seventh day.
耐碱性测试根据企业标准测试：将表面活性剂配置为10.0wt％水溶液，向其中慢慢加入40.0wt％NaOH水溶液，并持续搅拌，随时观察，当溶液变浑浊时，立即停止加入。The alkali resistance test is based on the corporate standard test: the surfactant is configured as a 10.0wt% aqueous solution, and 40.0wt% NaOH aqueous solution is slowly added to it, and the stirring is continued. Observe at any time. When the solution becomes turbid, stop adding immediately.
耐碱性的计算按下式进行：(1000×m 2)/m 3 The calculation of alkali resistance is carried out as follows: (1000×m 2 )/m 3
式中，m 2表示变浑浊时加入NaOH的质量，g；m 3表示变浑浊时水的质量，g。 In the formula, m 2 represents the mass of NaOH added when it becomes turbid, g; m 3 represents the mass of water when it becomes turbid, g.
粘度测试：条件：温度25℃，转速：20PRM，64转子，布洛克菲尔德粘度计。Viscosity test: conditions: temperature 25°C, speed: 20PRM, 64 rotor, Brookfield viscometer.
中间体转化率根据QB/T 2118-2012，测试产品中游离酰胺含量，再通过计算确定。The conversion rate of intermediates is determined according to QB/T 2118-2012, the free amide content in the product is tested, and then determined by calculation.
表1 为本发明妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的性能Table 1 shows the performance of the tall oil fatty acid imidazoline sulfonate surfactant of the present invention
Figure PCTCN2020114502-appb-000007
Figure PCTCN2020114502-appb-000007
如表1所示，妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的耐碱性大于300gNaOH/L(月桂酸咪唑啉耐碱性为200gNaOH/L左右)，耐碱性较好，固含量为35％时流动性良好。As shown in Table 1, the alkali resistance of tall oil fatty acid imidazoline sulfonate surfactant is greater than 300gNaOH/L (the alkali resistance of lauric acid imidazoline is about 200gNaOH/L), the alkali resistance is better, and the solid content is The fluidity is good at 35%.
本发明的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂是一种新型两性表面性剂，具有良好的去污、增溶和乳化性，耐强酸和强碱，有着优异的除蜡和缓蚀效果，对冲压油、防锈油和切削油等矿物油有着优异的乳化和油污剥离能力，适用于要求耐强酸(60％硫酸)和强碱(20％NaOH)、耐温的体系。The tall oil fatty acid imidazoline sulfonate surfactant of the present invention is a new type of amphoteric surface agent, which has good decontamination, solubilization and emulsification, resistance to strong acids and alkalis, and excellent wax removal and corrosion inhibition effects , It has excellent emulsification and oil removal ability for mineral oils such as stamping oil, anti-rust oil and cutting oil. It is suitable for systems that require strong acid (60% sulfuric acid) and strong alkali (20% NaOH) and temperature resistance.
实施例11Example 11
以羟乙基乙二胺为例，本发明的合成路线如下：Taking hydroxyethyl ethylene diamine as an example, the synthetic route of the present invention is as follows:
Figure PCTCN2020114502-appb-000008
Figure PCTCN2020114502-appb-000008
其中，R具体是：Among them, R is specifically:
油酸烷基基团：CH 3(CH 2) 7CH＝CH(CH 2) 7 - Oleic alkyl group: CH 3 (CH 2) 7 CH = CH (CH 2) 7 -
亚油酸烷基基团：CH 3(CH 2) 4CH＝CHCH 2CH＝CH(CH 2) 7 - Linoleic alkyl group: CH 3 (CH 2) 4 CH = CHCH 2 CH = CH (CH 2) 7 -
松香酸烷基基团：
Figure PCTCN2020114502-appb-000009
Rosin acid alkyl group:
Figure PCTCN2020114502-appb-000009
微量的饱和脂肪酸基团：如C16酸烷基部分、C18酸烷基部分，CH 3(CH 2) 14-CH 3(CH 2) 16-。 Trace amount of saturated fatty acid groups: such as C16 acid alkyl part, C18 acid alkyl part, CH 3 (CH 2 ) 14 -CH 3 (CH 2 ) 16 -.
在装有电动搅拌器、温度计、氮气导入管及减压蒸馏装置的1升四口烧瓶中，加入(1.5摩尔、156.3克)羟乙基乙二胺，在搅拌和氮气保护条件下加入(1摩尔、286.2克)妥尔油脂肪酸(kraton FA2)和0.9克磷酸，开动真空泵调节反应体系真空残压至150mmhg，升温至100℃开始计时，以20℃/h升温速率梯度升温至170℃反应2h，升温至220℃环化反应2h，无水蒸出后测酸值为2.4mgKOH/g，妥尔油脂肪酸(kraton FA2)转化率为98.5％，把真空提高至2mmhg，把过量的羟乙基乙二胺蒸馏出，降温至90℃，得到妥尔油酸咪唑啉中间体355.3克，二酰胺含量为2.5％。In a 1-liter four-necked flask equipped with an electric stirrer, a thermometer, a nitrogen introduction tube and a vacuum distillation device, add (1.5 moles, 156.3 g) hydroxyethyl ethylene diamine, add (1 Mol, 286.2g) tall oil fatty acid (kraton FA2) and 0.9g phosphoric acid, turn on the vacuum pump to adjust the vacuum residual pressure of the reaction system to 150mmhg, start timing when the temperature is raised to 100°C, and increase the temperature to 170°C at a heating rate of 20°C/h for 2h , The temperature was raised to 220°C for cyclization reaction for 2h, the acid value measured after anhydrous steaming was 2.4mgKOH/g, the conversion rate of tall oil fatty acid (kraton FA2) was 98.5%, the vacuum was increased to 2mmhg, and the excess hydroxyethyl Ethylenediamine was distilled out, and the temperature was lowered to 90°C to obtain 355.3 g of a tall oil acid imidazoline intermediate with a diamide content of 2.5%.
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)上述妥尔油酸咪唑啉中间体、132.4克去离子水、21.2克乙二醇和(0.2摩尔、8克)氢氧化钠，升温至90℃，再加入(0.2摩尔、39.3克)3-氯-2-羟基丙磺酸钠，反应5h，测得氯离子转化率为99.9％，妥尔油酸咪唑啉中间体转化率为92.6％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-neck flask equipped with an electric stirrer, thermometer, and condenser, add (0.1 mole, 35.4 g) the tall oil acid imidazoline intermediate, 132.4 g deionized water, 21.2 g ethylene glycol and (0.2 mole , 8g) sodium hydroxide, heated to 90℃, then added (0.2mol, 39.3g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 5h, the chloride ion conversion rate was 99.9%, tall oil The conversion rate of the acid imidazoline intermediate was 92.6%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
妥尔油脂肪酸和妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的红外光谱如图2所示，图2为本发明实施例11制备的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的红外谱图。其中2922cm -1附近为C-H的振动吸收峰；2852cm -1附近为C-N的振动吸收峰；2852cm -1处附近为CH 2中C-H键的对称伸缩振动；1708cm -1处的吸收峰为COOH上的羰基振动峰；1626cm -1附近的吸收峰为C＝O特征吸收峰；说明季铵化反应时妥尔油酸咪唑啉环水解；1190cm -1为磺酸基的特征吸收峰，官能团特征与产物结构相符，表明成功合成了妥尔油脂肪酸咪唑啉磺酸盐表面活性剂。 The infrared spectra of tall oil fatty acid and tall oil fatty acid imidazoline sulfonate surfactants are shown in Figure 2. Figure 2 is the infrared spectra of tall oil fatty acid imidazoline sulfonate surfactants prepared in Example 11 of the present invention Spectrogram. Wherein the vibration near 2922cm -1 CH absorption peak; CN near 2852cm -1 vibration absorption peak; the vicinity of 2852cm -1 of the symmetric stretching vibration of CH 2 CH bond; absorption peak at 1708cm -1 for the COOH, The carbonyl vibration peak; the absorption peak near 1626 cm -1 is the characteristic absorption peak of C=O; it shows that the tall oil imidazoline ring is hydrolyzed during the quaternization reaction; 1190 cm -1 is the characteristic absorption peak of the sulfonic acid group, the characteristics of the functional group and the product The structure is consistent, indicating that the tall oil fatty acid imidazoline sulfonate surfactant was successfully synthesized.
实施例12Example 12
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例11制备得到的妥尔油酸咪唑啉中间体、114克去离子水、17.7克乙醇和(0.15摩尔、6克)氢氧化钠，升温至80℃，再加入(0.15摩尔、29.5克)3-氯-2-羟基丙磺酸钠，反应6h，测得氯离子转化率为99.7％，妥尔油酸咪唑啉中间体转化率为93.5％，得到妥尔油脂肪酸咪 唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, a thermometer, and a condenser, add (0.1 mole, 35.4 g) the tall oil imidazoline intermediate prepared in Example 11, 114 g of deionized water, and 17.7 g of ethanol. And (0.15 mol, 6 g) sodium hydroxide, heated to 80°C, and then (0.15 mol, 29.5 g) sodium 3-chloro-2-hydroxypropanesulfonate (0.15 mol, 29.5 g) was added, reacted for 6 hours, and the chloride ion conversion rate was 99.7% The conversion rate of the tall oil acid imidazoline intermediate was 93.5%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例13Example 13
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例11制备得到的妥尔油酸咪唑啉中间体、99.9克去离子水、14.2克甲醇和(0.15摩尔、6克)氢氧化钠，升温至70℃，再加入(0.11摩尔、21.6克)3-氯-2-羟基丙磺酸钠，反应7h，测得氯离子转化率为99.5％，妥尔油酸咪唑啉中间体转化率为92.1％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, a thermometer, and a condenser, add (0.1 mole, 35.4 g) the tall oil acid imidazoline intermediate prepared in Example 11, 99.9 g of deionized water, and 14.2 g of methanol. And (0.15 mol, 6 g) sodium hydroxide, heated to 70°C, then (0.11 mol, 21.6 g) sodium 3-chloro-2-hydroxypropanesulfonate was added, reacted for 7 hours, and the chloride ion conversion rate was determined to be 99.5% The conversion rate of the tall oil acid imidazoline intermediate was 92.1%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例14Example 14
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例11制备得到的妥尔油酸咪唑啉中间体、115克去离子水、21.2克乙二醇和(0.15摩尔、8.4克)氢氧化钾，升温至80℃，再加入(0.15摩尔、29.5克)3-氯-2-羟基丙磺酸钠，反应6h，测得氯离子转化率为99.3％，妥尔油酸咪唑啉中间体转化率为93.4％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, a thermometer, and a condenser, add (0.1 mole, 35.4 g) the tall oil imidazoline intermediate prepared in Example 11, 115 g of deionized water, and 21.2 g of ethyl acetate. Diol and (0.15 mol, 8.4 g) potassium hydroxide, heated to 80 ℃, and then added (0.15 mol, 29.5 g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 6 hours, the chloride ion conversion rate was 99.3 %, the conversion rate of the tall oil acid imidazoline intermediate was 93.4%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例15Example 15
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例11制备得到的妥尔油酸咪唑啉中间体、142克去离子水、17.7克异丙醇和(0.2摩尔、11.2克)氢氧化钾，升温至70℃，再加入(0.2摩尔、39.3克)3-氯-2-羟基丙磺酸钠，反应7h，测得氯离子转化率为99.4％，妥尔油酸咪唑啉中间体转化率为94.7％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500 mL four-necked flask equipped with an electric stirrer, a thermometer, and a condenser, add (0.1 mole, 35.4 g) the tall oil acid imidazoline intermediate prepared in Example 11, 142 g of deionized water, and 17.7 g of isophthalic acid. Propanol and (0.2 mol, 11.2 g) potassium hydroxide were heated to 70° C., and then (0.2 mol, 39.3 g) sodium 3-chloro-2-hydroxypropanesulfonate was added, reacted for 7 hours, and the chloride ion conversion rate was determined to be 99.4 %, the conversion rate of the tall oil acid imidazoline intermediate is 94.7%, and the tall oil fatty acid imidazoline sulfonate surfactant is obtained with a solid content of 35%.
实施例16Example 16
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实施例11制备得到的妥尔油酸咪唑啉中间体、103.3克去离子水、14.2克甲醇和(0.11摩尔、6.2克)氢氧化钾，升温至60℃，再加入(0.11摩尔、21.6克)3-氯-2-羟基丙磺酸钠，反应8h，测得氯离子转化率为99.2％，妥尔油酸咪唑啉中间体转化率为90.3％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500 mL four-necked flask equipped with an electric stirrer, a thermometer, and a condenser, add (0.1 mole, 35.4 g) the tall oil acid imidazoline intermediate prepared in Example 11, 103.3 g deionized water, and 14.2 g methanol And (0.11mol, 6.2g) potassium hydroxide, heated to 60℃, then added (0.11mol, 21.6g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 8h, the conversion rate of chloride ion was measured to be 99.2% The conversion rate of the tall oil acid imidazoline intermediate was 90.3%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例17Example 17
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.4克)实 施例11制备得到的妥尔油酸咪唑啉中间体、137克去离子水、21.2克乙醇和(0.1摩尔、10.6克)碳酸钠，升温至90℃，再加入(0.2摩尔、39.3克)3-氯-2-羟基丙磺酸钠，反应6h，测得氯离子转化率为98.9％，妥尔油酸咪唑啉中间体转化率为92.2％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-neck flask equipped with an electric stirrer, a thermometer and a condenser, add (0.1 mole, 35.4 g) the tall oil imidazoline intermediate prepared in Example 11, 137 g of deionized water, and 21.2 g of ethanol. And (0.1 mol, 10.6 g) sodium carbonate, heated to 90°C, then added (0.2 mol, 39.3 g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 6 hours, and the chloride ion conversion rate was 98.9%. The conversion rate of the tall oil acid imidazoline intermediate was 92.2%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例18Example 18
在装有电动搅拌器、温度计、氮气导入管及减压蒸馏装置的1升四口烧瓶中，加入(1.2摩尔、123.8克)二乙烯三胺，在搅拌和氮气保护条件下加入(1摩尔、286.2克)妥尔油脂肪酸(kraton FA2)和0.8克磷酸，开动真空泵调节反应体系真空残压至180mmhg，升温至100℃开始计时，以20℃/h升温速率梯度升温至170℃反应2h，升温至220℃环化反应3h，无水蒸出后测酸值为1.8mgKOH/g，妥尔油脂肪酸(kraton FA2)转化率为98.9％，把真空提高至3mmhg，把过量的二乙烯三胺蒸馏出，降温至90℃，得到妥尔油酸咪唑啉中间体356.3克。In a 1-liter four-necked flask equipped with an electric stirrer, a thermometer, a nitrogen introduction tube and a vacuum distillation device, add (1.2 moles, 123.8 g) diethylene triamine, add (1 mole, 286.2g) tall oil fatty acid (kraton FA2) and 0.8g phosphoric acid, turn on the vacuum pump to adjust the vacuum residual pressure of the reaction system to 180mmhg, start timing when the temperature is raised to 100°C, and react with a gradient of 20°C/h to 170°C and react for 2h. The cyclization reaction is at 220℃ for 3h, the acid value is 1.8mgKOH/g after anhydrous distillation, the conversion rate of tall oil fatty acid (kraton FA2) is 98.9%, the vacuum is increased to 3mmhg, and the excess diethylenetriamine is distilled The temperature was lowered to 90°C to obtain 356.3 grams of tall oil acid imidazoline intermediate.
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.3克)上述妥尔油酸咪唑啉中间体、132.1克去离子水、21.2克乙二醇和(0.2摩尔、8克)氢氧化钠，升温至80℃，再加入(0.2摩尔、39.3克)3-氯-2-羟基丙磺酸钠，反应6h，测得氯离子转化率为99.7％，妥尔油酸咪唑啉中间体转化率为92.8％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, thermometer, and condenser, add (0.1 mole, 35.3 grams) the tall oil acid imidazoline intermediate, 132.1 grams of deionized water, 21.2 grams of ethylene glycol and (0.2 moles) , 8g) sodium hydroxide, heated to 80°C, then added (0.2mol, 39.3g) sodium 3-chloro-2-hydroxypropanesulfonate, reacted for 6h, the measured chloride ion conversion rate was 99.7%, tall oil The conversion rate of the acid imidazoline intermediate was 92.8%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
实施例19Example 19
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.3克)实施例18制备得到的妥尔油酸咪唑啉中间体、114.7克去离子水、21.2克乙醇，升温至70℃，再加入(0.15摩尔、29.5克)3-氯-2-羟基丙磺酸钠和(0.15摩尔、8.4克)氢氧化钾，反应7h，测得氯离子转化率为99.5％，妥尔油酸咪唑啉中间体转化率为92.5％，得到妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，固含量为35％。In a 500mL four-necked flask equipped with an electric stirrer, a thermometer and a condenser, add (0.1 mole, 35.3 grams) the tall oil imidazoline intermediate prepared in Example 18, 114.7 grams of deionized water, and 21.2 grams of ethanol. , The temperature was raised to 70°C, and then (0.15 mol, 29.5 g) sodium 3-chloro-2-hydroxypropanesulfonate and (0.15 mol, 8.4 g) potassium hydroxide were added, reacted for 7 hours, and the chloride ion conversion rate was determined to be 99.5% , The conversion rate of the tall oil acid imidazoline intermediate is 92.5%, and the tall oil fatty acid imidazoline sulfonate surfactant is obtained with a solid content of 35%.
实施例20Example 20
在装有电动搅拌器、温度计、冷凝管的500mL四口瓶中，加入(0.1摩尔、35.3克)实施例18制备得到的妥尔油酸咪唑啉中间体、140.5克去离子水、17.7克异丙醇和(0.1摩尔、10.6克)碳酸钠，升温至90℃，再加入(0.2摩尔、39.3克)3-氯-2-羟基丙磺酸钠，反应6h，测得氯离子转化率为99.0％，妥尔油酸咪唑啉中间体转化率为91.2％，得到妥尔油脂肪酸咪 唑啉磺酸盐表面活性剂，固含量为35％。In a 500 mL four-necked flask equipped with an electric stirrer, a thermometer, and a condenser, add (0.1 mole, 35.3 grams) the tall oil imidazoline intermediate prepared in Example 18, 140.5 grams of deionized water, and 17.7 grams of isophthalic acid. Propanol and (0.1 mol, 10.6 g) sodium carbonate were heated to 90°C, and then (0.2 mol, 39.3 g) sodium 3-chloro-2-hydroxypropanesulfonate was added, reacted for 6 hours, and the chloride ion conversion rate was measured to be 99.0% The conversion rate of the tall oil acid imidazoline intermediate was 91.2%, and the tall oil fatty acid imidazoline sulfonate surfactant was obtained with a solid content of 35%.
对比例2Comparative example 2
S.-F.Wang等以妥尔油脂肪酸和羟乙基乙二胺为原料，用二甲苯做携水剂，合成了妥尔油酸咪唑啉中间体，再与3-氯-2-羟基丙磺酸钠合成妥尔油酸磺酸盐。妥尔油酸咪唑啉中间体中的二酰胺副产物含量太高，得到的产品色泽较深和稳定性较差，并且用二甲苯作溶剂，二甲苯是3类致癌溶剂，不利于工业化推广。S.-F.Wang et al. used tall oil fatty acid and hydroxyethyl ethylenediamine as raw materials, and used xylene as a water-carrying agent to synthesize a tall oil acid imidazoline intermediate, which was then combined with 3-chloro-2-hydroxyl Sodium propanesulfonate synthesizes tall oil sulfonate. The content of diamide by-product in the intermediate of tall oil acid imidazoline is too high, the product obtained has a darker color and poor stability, and xylene is used as a solvent, which is a type 3 carcinogenic solvent, which is not conducive to industrialization.
制备方法：中间体HEAI合成：装有搅拌器、回流冷凝器、分水器和温度计的四口烧瓶加入56.4g(0.2mol)妥尔油脂肪酸，0.2mol羟乙基乙二胺和100毫升二甲苯。反应物在140-150℃回流至没有更多的水从分水器流出。拆除分水器，将反应体系压力调整到14.66kPa，反应温度提高到250℃，反应30min，得到半固体的妥尔油咪唑啉中间体HEAI，二酰胺含量：4.1％。Preparation method: Synthesis of intermediate HEAI: a four-necked flask equipped with a stirrer, reflux condenser, water separator and thermometer is added 56.4g (0.2mol) tall oil fatty acid, 0.2mol hydroxyethylethylenediamine and 100ml diamine Toluene. The reactants are refluxed at 140-150°C until no more water flows out of the trap. The water trap was removed, the pressure of the reaction system was adjusted to 14.66 kPa, the reaction temperature was increased to 250° C., and the reaction was conducted for 30 minutes to obtain the semi-solid tall oil imidazoline intermediate HEAI with a diamide content: 4.1%.
季铵化：三口烧瓶中加入去离子水20ml，10.5g(0.03mol)的HEAI以及5.9g(0.03mol)3-氯-2-羟基丙磺酸盐，加热至80-90℃。在搅拌下，缓慢加入10％水溶液氢氧化钠(约12ml)。直到反应混合物的pH值下降到7-8。然后对合成的混合物进行干燥，在真空状态下，把水抽走。再用50ml无水乙醇溶解干燥产物，过滤除去未溶解的NaCl。滤液经蒸馏回收酒精，得到淡黄色透明半固体。Quaternization: Add 20ml of deionized water, 10.5g (0.03mol) of HEAI and 5.9g (0.03mol) of 3-chloro-2-hydroxypropanesulfonate into a three-necked flask, and heat to 80-90°C. While stirring, slowly add 10% aqueous sodium hydroxide (about 12 ml). Until the pH of the reaction mixture drops to 7-8. The synthesized mixture is then dried, and the water is pumped away under vacuum. Then use 50ml of absolute ethanol to dissolve the dried product, and filter to remove the undissolved NaCl. The filtrate is distilled to recover alcohol to obtain a light yellow transparent semi-solid.
实施例11～20及对比例2制备的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的性能测试如表2所示，生物降解度根据GB/T 15818-2006表面活性剂生物降解度的试验方法进行测试(泡沫法测定，第七天的降解度。The performance test of the tall oil fatty acid imidazoline sulfonate surfactant prepared in Examples 11-20 and Comparative Example 2 is shown in Table 2. The degree of biodegradation is based on the test of GB/T 15818-2006 Surfactant Biodegradability Method for testing (determined by foam method, degree of degradation on the seventh day.
耐碱性测试根据企业标准测试：将表面活性剂配置为10.0wt％水溶液，向其中慢慢加入40.0wt％NaOH水溶液，并持续搅拌，随时观察，当溶液变浑浊时，立即停止加入。The alkali resistance test is based on the corporate standard test: the surfactant is configured as a 10.0wt% aqueous solution, and 40.0wt% NaOH aqueous solution is slowly added to it, and the stirring is continued. Observe at any time. When the solution becomes turbid, stop adding immediately.
耐碱性的计算按下式进行：(1000×m 2)/m 3 The calculation of alkali resistance is carried out as follows: (1000×m 2 )/m 3
式中，m 2表示变浑浊时加入NaOH的质量，g；m 3表示变浑浊时水的质量，g。 In the formula, m 2 represents the mass of NaOH added when it becomes turbid, g; m 3 represents the mass of water when it becomes turbid, g.
粘度测试：条件：温度25℃，转速：20PRM，64转子，布洛克菲尔德粘度计。Viscosity test: conditions: temperature 25°C, speed: 20PRM, 64 rotor, Brookfield viscometer.
中间体转化率根据QB/T 2118-2012，测试产品中游离酰胺含量，再通过计算确定。The conversion rate of intermediates is determined according to QB/T 2118-2012, the free amide content in the product is tested, and then determined by calculation.
表2 为本发明妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的性能Table 2 is the performance of the tall oil fatty acid imidazoline sulfonate surfactant of the present invention
Figure PCTCN2020114502-appb-000010
Figure PCTCN2020114502-appb-000010
Figure PCTCN2020114502-appb-000011
Figure PCTCN2020114502-appb-000011
如表2所示，妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的耐碱性大于300gNaOH/L(月桂酸咪唑啉耐碱性为200gNaOH/L左右)，耐碱性较好，固含量为35％时流动性良好。As shown in Table 2, the alkali resistance of tall oil fatty acid imidazoline sulfonate surfactant is greater than 300gNaOH/L (the alkali resistance of lauric acid imidazoline is about 200gNaOH/L), the alkali resistance is better, and the solid content is The fluidity is good at 35%.
本发明的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂是一种新型两性表面性剂，具有良好的去污、增溶和乳化性，耐强酸和强碱，有着优异的除蜡和缓蚀效果，对冲压油、防锈油和切削油等矿物油有着优异的乳化和油污剥离能力，适用于要求耐强酸(60％硫酸)和强碱(20％NaOH)、耐温的体系。The tall oil fatty acid imidazoline sulfonate surfactant of the present invention is a new type of amphoteric surface agent, which has good decontamination, solubilization and emulsification, resistance to strong acids and alkalis, and excellent wax removal and corrosion inhibition effects , It has excellent emulsification and oil removal ability for mineral oils such as stamping oil, anti-rust oil and cutting oil. It is suitable for systems that require strong acid (60% sulfuric acid) and strong alkali (20% NaOH) and temperature resistance.
以上所述仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何熟悉本专利的技术人员在不脱离本发明技术方案范围内，当可利用上述提示的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明方案的范围内。The above are only preferred embodiments of the present invention, and do not limit the present invention in any form. Although the present invention has been disclosed as above in preferred embodiments, it is not intended to limit the present invention. Any technology familiar with this patent Without departing from the scope of the technical solution of the present invention, personnel can use the technical content suggested above to make slight changes or modification into equivalent embodiments with equivalent changes, but any content that does not deviate from the technical solution of the present invention is based on the technology of the present invention. Essentially, any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the present invention.

Claims (17)

  1. 一种妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，其特征在于，主要成分结构式如下：A tall oil fatty acid imidazoline sulfonate surfactant, which is characterized in that the main component structural formula is as follows:
    Figure PCTCN2020114502-appb-100001
    Figure PCTCN2020114502-appb-100001
    其中，R为油酸烷基基团、亚油酸烷基基团、松香酸烷基基团、饱和脂肪酸基团。Among them, R is an oleic acid alkyl group, a linoleic acid alkyl group, a rosin acid alkyl group, and a saturated fatty acid group.
  2. 根据权利要求1所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，其特征在于，所述结构式中：The tall oil fatty acid imidazoline sulfonate surfactant according to claim 1, wherein in the structural formula:
    油酸烷基基团：CH 3(CH 2) 7CH＝CH(CH 2) 7 - Oleic alkyl group: CH 3 (CH 2) 7 CH = CH (CH 2) 7 -
    亚油酸烷基基团：CH 3(CH 2) 4CH＝CHCH 2CH＝CH(CH 2) 7 - Linoleic alkyl group: CH 3 (CH 2) 4 CH = CHCH 2 CH = CH (CH 2) 7 -
    松香酸烷基基团：
    Figure PCTCN2020114502-appb-100002
    Rosin acid alkyl group:
    Figure PCTCN2020114502-appb-100002
    饱和脂肪酸基团：CH 3(CH 2) 14- CH 3(CH 2) 16-。 Saturated fatty acid group: CH 3 (CH 2 ) 14 -CH 3 (CH 2 ) 16 -.
  3. 根据权利要求1所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂，其特征在于，固含量为30-40％。The tall oil fatty acid imidazoline sulfonate surfactant according to claim 1, wherein the solid content is 30-40%.
  4. 一种权利要求1至3任一项所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，包括以下步骤：A method for preparing a tall oil fatty acid imidazoline sulfonate surfactant according to any one of claims 1 to 3, characterized in that it comprises the following steps:
    第一步，妥尔油酸咪唑啉中间体的合成：The first step is the synthesis of tall oil acid imidazoline intermediates:
    在氮气保护下，将妥尔油脂肪酸、有机多胺混合，加入磷酸作为催化剂，所述妥尔油脂肪酸、有机多胺、磷酸的摩尔比为1:(0.5～2):(0.005～0.05)，调节反应体系真空残压至20～300mmhg，然后梯度升温反应，直至无水蒸出为止，测量酸值，调整真空，蒸馏出过量的原料，降温，获得所述妥尔油酸咪唑啉中间体；Under the protection of nitrogen, the tall oil fatty acid and organic polyamine are mixed, and phosphoric acid is added as a catalyst. The molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1:(0.5-2):(0.005-0.05) , Adjust the vacuum residual pressure of the reaction system to 20-300mmhg, and then react with gradient heating until the anhydrous is evaporated, measure the acid value, adjust the vacuum, distill out excess raw materials, and cool down to obtain the tall oil acid imidazoline intermediate ；
    第二步，季铵化反应：将第一步获得的妥尔油酸咪唑啉中间体、碱、去离子水混合，妥尔油酸咪唑啉中间体、碱、去离子水的质量比为1:(0.1～0.4):(2～10)，温度为40～100℃的条件下与烷基磺酸钠反应，所述妥尔油酸咪唑啉中间体和烷基磺酸钠的摩尔比为1:(1～3)，反应至氯离子含量不再变化，得到所述妥尔油脂肪酸咪唑啉磺酸盐表面活性剂。The second step is the quaternization reaction: the tall oil acid imidazoline intermediate obtained in the first step, alkali, and deionized water are mixed, and the mass ratio of tall oil imidazoline intermediate, alkali, and deionized water is 1 :(0.1～0.4):(2～10), react with sodium alkylsulfonate at a temperature of 40～100℃, the molar ratio of the intermediate of tall oil acid imidazoline and sodium alkylsulfonate is 1: (1 to 3), react until the chloride ion content no longer changes to obtain the tall oil fatty acid imidazoline sulfonate surfactant.
  5. 根据权利要求4所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述有机多胺为羟乙基乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中的至少一种；The method for preparing a tall oil fatty acid imidazoline sulfonate surfactant according to claim 4, wherein the organic polyamine is hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine, At least one of tetraethylenepentamine;
    所述妥尔油脂肪酸、有机多胺、磷酸的摩尔比为1:(1.1～1.5):(0.005～0.01)。The molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1: (1.1 to 1.5): (0.005 to 0.01).
  6. 根据权利要求4所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述梯度升温反应是指从室温升温至90～110℃，以5～25℃/h升温速率梯度升温至160～180℃反应1～48h，升温至210～250℃环化反应1～48h；The method for preparing a tall oil fatty acid imidazoline sulfonate surfactant according to claim 4, characterized in that, the gradient heating reaction refers to heating from room temperature to 90-110°C at a rate of 5-25°C/h The heating rate is gradually increased to 160～180℃ for 1～48h, and the temperature is increased to 210～250℃ for 1～48h for the cyclization reaction;
    所述酸值为中间体酸值小于3mgKOH/g。The acid value of the intermediate acid value is less than 3 mgKOH/g.
  7. 根据权利要求4所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述调整真空为2～3mmhg；The method for preparing a tall oil fatty acid imidazoline sulfonate surfactant according to claim 4, wherein the adjusted vacuum is 2 to 3 mmhg;
    所述降温是指温度为80～100℃。The cooling means that the temperature is 80-100°C.
  8. 根据权利要求4所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述碱为NaOH、KOH或Na 2CO 3； The method for preparing a tall oil fatty acid imidazoline sulfonate surfactant according to claim 4, wherein the alkali is NaOH, KOH or Na 2 CO 3 ;
    所述妥尔油酸咪唑啉中间体、碱、去离子水的质量比为1:(0.1～0.4):(3～5)。The mass ratio of the tall oil acid imidazoline intermediate, alkali, and deionized water is 1:(0.1-0.4):(3-5).
  9. 根据权利要求4所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述妥尔油酸咪唑啉中间体和烷基磺酸钠的摩尔比为1:(1.1～2)。The method for preparing tall oil fatty acid imidazoline sulfonate surfactant according to claim 4, wherein the molar ratio of the tall oil imidazoline intermediate to sodium alkyl sulfonate is 1:( 1.1～2).
  10. 根据权利要求4所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述烷基磺酸钠为3-氯-2-羟基丙磺酸钠、2-溴乙基磺酸钠、2-氯乙基磺酸钠、烯丙基磺酸钠。The method for preparing tall oil fatty acid imidazoline sulfonate surfactant according to claim 4, wherein the sodium alkyl sulfonate is sodium 3-chloro-2-hydroxypropanesulfonate, 2-bromo Sodium ethyl sulfonate, sodium 2-chloroethyl sulfonate, sodium allyl sulfonate.
  11. 一种权利要求1至3任一项所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，包括以下步骤：A method for preparing a tall oil fatty acid imidazoline sulfonate surfactant according to any one of claims 1 to 3, characterized in that it comprises the following steps:
    第一步，妥尔油酸咪唑啉中间体的合成：The first step is the synthesis of tall oil acid imidazoline intermediates:
    在氮气保护下，将妥尔油脂肪酸、有机多胺混合，加入磷酸作为催化剂，所述妥尔油脂肪酸、有机多胺、磷酸的摩尔比为1:(0.5～2):(0.005～0.05)，调节反应体系真空残压至20～300mmhg，然后梯度升温反应，直至无水蒸出为止，测量酸值，调整真空，蒸馏出过量的原料，降温，获得所述妥尔油酸咪唑啉中间体；Under the protection of nitrogen, the tall oil fatty acid and organic polyamine are mixed, and phosphoric acid is added as a catalyst. The molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1:(0.5-2):(0.005-0.05) , Adjust the vacuum residual pressure of the reaction system to 20-300mmhg, and then react with gradient heating until the anhydrous is evaporated, measure the acid value, adjust the vacuum, distill out excess raw materials, and cool down to obtain the tall oil acid imidazoline intermediate ；
    第二步，季铵化反应：将第一步获得的妥尔油酸咪唑啉中间体、低碳醇、碱、去离子水混合，妥尔油酸咪唑啉中间体、低碳醇、碱、去离子水的质量比为1:(0.01～1):(0.1～0.4):(2～10)，温度为40～100℃的条件下与烷基磺酸钠反应，所述妥尔油酸咪唑啉中间体和烷基磺酸钠的摩尔比为1:(1～3)，反应至氯离子含量不再变化，得到所述妥尔油脂肪酸咪唑啉磺酸盐表面活性剂。The second step is the quaternization reaction: the tall oil acid imidazoline intermediate obtained in the first step, lower alcohol, alkali, and deionized water are mixed, tall oil acid imidazoline intermediate, lower alcohol, alkali, The mass ratio of deionized water is 1:(0.01～1):(0.1～0.4):(2～10), and it reacts with sodium alkyl sulfonate at a temperature of 40～100℃, the tall oil acid The molar ratio of the imidazoline intermediate to the sodium alkyl sulfonate is 1: (1-3), and the reaction is performed until the chloride ion content no longer changes to obtain the tall oil fatty acid imidazoline sulfonate surfactant.
  12. 根据权利要求11所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述有机多胺为羟乙基乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中的至少一种；The method for preparing tall oil fatty acid imidazoline sulfonate surfactant according to claim 11, wherein the organic polyamine is hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine, At least one of tetraethylenepentamine;
    所述妥尔油脂肪酸、有机多胺、磷酸的摩尔比为1:(1.1～1.5):(0.005～0.01)。The molar ratio of the tall oil fatty acid, organic polyamine, and phosphoric acid is 1: (1.1 to 1.5): (0.005 to 0.01).
  13. 根据权利要求11所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征 在于，所述梯度升温反应是指从室温升温至90～110℃，以5～25℃/h升温速率梯度升温至160～180℃反应1～48h，升温至210～250℃环化反应1～48h；The method for preparing a tall oil fatty acid imidazoline sulfonate surfactant according to claim 11, characterized in that the gradient heating reaction refers to heating from room temperature to 90-110°C at a rate of 5-25°C/h The heating rate is gradually increased to 160～180℃ for 1～48h, and the temperature is increased to 210～250℃ for 1～48h for the cyclization reaction;
    所述酸值为中间体酸值小于3mgKOH/g；The acid value of the intermediate acid value is less than 3mgKOH/g;
    所述调整真空为2～3mmhg。The adjusted vacuum is 2 to 3 mmhg.
  14. 根据权利要求11所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述降温是指温度为80～100℃；The method for preparing a tall oil fatty acid imidazoline sulfonate surfactant according to claim 11, wherein the cooling means that the temperature is 80-100°C;
    所述低碳醇为甲醇、乙醇、异丙醇或乙二醇；The lower alcohol is methanol, ethanol, isopropanol or ethylene glycol;
    所述碱为NaOH、KOH或Na 2CO 3。 The base is NaOH, KOH or Na 2 CO 3 .
  15. 根据权利要求11所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述妥尔油酸咪唑啉中间体、低碳醇、碱、去离子水的质量比为1:(0.4～0.6):(0.1～0.4):(2.5～4)。The method for preparing a tall oil fatty acid imidazoline sulfonate surfactant according to claim 11, wherein the mass ratio of the tall oil imidazoline intermediate, lower alcohol, alkali, and deionized water is It is 1:(0.4～0.6):(0.1～0.4):(2.5～4).
  16. 根据权利要求11所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述烷基磺酸钠为3-氯-2-羟基丙磺酸钠、2-溴乙基磺酸钠、2-氯乙基磺酸钠、烯丙基磺酸钠。The method for preparing tall oil fatty acid imidazoline sulfonate surfactant according to claim 11, wherein the sodium alkyl sulfonate is sodium 3-chloro-2-hydroxypropanesulfonate, 2-bromo Sodium ethyl sulfonate, sodium 2-chloroethyl sulfonate, sodium allyl sulfonate.
  17. 根据权利要求11所述的妥尔油脂肪酸咪唑啉磺酸盐表面活性剂的制备方法，其特征在于，所述妥尔油酸咪唑啉中间体和烷基磺酸钠的摩尔比为1:(1.1～2)。The method for preparing tall oil fatty acid imidazoline sulfonate surfactant according to claim 11, wherein the molar ratio of the tall oil imidazoline intermediate to sodium alkyl sulfonate is 1:( 1.1～2).
PCT/CN2020/114502 2019-09-11 2020-09-10 Tall oil fatty acid imidazoline sulfonate surfactant and preparation method therefor WO2021047588A1 (en)

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